Advancements in osmotically driven membrane systems including multi-stage purification

Information

  • Patent Grant
  • 12005396
  • Patent Number
    12,005,396
  • Date Filed
    Thursday, November 14, 2019
    4 years ago
  • Date Issued
    Tuesday, June 11, 2024
    3 months ago
Abstract
An example water purification system for purifying high concentration feed solutions includes a high rejection forward osmosis module, one or more low rejection modules, and a high rejection reverse osmosis module. The low rejection modules may have different rejection levels. The system may be pressurized by one or more pumps. One or more of the low rejection modules may include one or more nanofiltration (NF) membranes. The draw solution may comprise a monovalent salt, a multivalent salt, or a combination of both.
Description
TECHNICAL FIELD

Examples described herein relate to separation systems, elements, and methods which may be used for forward osmosis (FO) or reverse osmosis (RO), or generally any separation process.


BACKGROUND

For osmotic pre-treatment, higher draw solution osmotic potential substantially increases the system's operating window of feed concentration. Conventional systems typically have a limit on draw solution concentration for reverse osmosis (RO).


In RO systems, the maximum feed salinity treatable is limited by the maximum salinity of the draw solution. The draw solution is typically limited to a high point of 80,000 ppm, as any greater concentration would require a RO hydrostatic pressure that would rupture the membrane. Maximum RO operation hydrostatic pressure is typically between 1000 and 1200 psi. The following generally explains this limitation. The flux across the RO membrane is proportional to the active membrane pressure. The active membrane pressure is the difference in hydrostatic pressure across the RO membrane (typically 800 psi feed to near atmosphere permeate) less the difference in osmotic pressure across the RO membrane (typically 500 psi feed to near 0 psi permeate). The active membrane pressure may be adjusted by changing any of the aforementioned values. While the osmotic pressure of the feed is easily adjustable in the system, the osmotic pressure of the permeate is typically fixed near zero, and is a function of the rejection of the RO membrane (defined as one minus the fraction of salt that passes into the permeate, typical RO rejections are greater than 99%).


Consequently, purification systems that are capable of treating feed solutions in excess concentrations of 80,000 ppm typically use heat and phase change, resulting in large foot prints, high energy demands and high capital system costs compared to membrane driven systems. These systems are used when the feed total dissolved solute (TDS) is greater than 80,000 ppm, or when lower TDS feed solutions must be treated to high recoveries with rejects exceeding 80,000 ppm (e.g., zero liquid discharge applications).


SUMMARY

Examples of apparatuses, systems, and methods for purification are disclosed herein. For example, an apparatus may include a forward osmosis module which may receive a feed stream and a high concentration draw stream to produce a first stream; a pump which may pressurize the first stream; a low rejection membrane module which may receive the pressurized first stream to produce the high concentration draw stream and a low concentration stream; and a reverse osmosis module which may receive the low concentration stream to produce a product stream and a reject stream. The reject stream from the reverse osmosis stream may be combined with the first stream and provided to the low rejection module. The draw stream may include a multivalent salt.


An example system may include a forward osmosis stage which may be configured to receive a draw stream and a feed stream to produce a first stream; a plurality of low rejection stages connected in series which may be configured to receive the first stream and produce an output stream; and a reverse osmosis stage which may receive the output stream to produce a reject stream and a product stream. The low rejection stages may each produce a reject stream and provide the reject stream to the previous low rejection stage.


A further example, a method may include providing a draw stream to a forward osmosis module; providing a feed stream to the forward osmosis module; filtering the feed stream with the forward osmosis module which may produce a first stream; pressurizing the first stream; filtering the pressurized first stream with a low rejection module which may produce a dilute stream; and filtering the dilute stream with a reverse osmosis module which may produce a product stream. The method may further include adding anti-scalants or anti-foulants to the feed stream.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a block diagram of a purification system according to an embodiment of the invention.



FIG. 2 is a block diagram of a purification system according to another embodiment of the invention.



FIG. 3 is a block diagram of a purification system according to a further embodiment of the invention.





DETAILED DESCRIPTION

Certain details are set forth below to provide a sufficient understanding of embodiments of the invention. However, it will be clear to one skilled in the art that embodiments of the invention may be practiced without various of these particular details. In some instances, well-known chemical structures, chemical components, molecules, materials, manufacturing components, control systems, electronic components, timing protocols, and software operations have not been shown in detail in order to avoid unnecessarily obscuring the described embodiments of the invention.


In examples described herein, existing limits on draw solution concentration for reverse osmosis (RO) and high pressure RO may be overcome using nanofiltration (NF) and/or RO membrane modules staged in an array of two or more modules deep, and allowing increased salt concentrations on the permeate side of the NF or RO membrane in upstream stages. In this way, the effective concentration differential across each RO membrane is reduced along with the required applied hydraulic pressure. The increased salt concentration on the permeate side of the RO membrane can be produced in several ways, including utilizing less selective RO membranes or a style of RO membrane with 4 ports (e.g., draw in/out, permeate in/out). This staging of RO modules is typically not done because of the multiplicative nature of recoveries, meaning that total system recovery may be very low. Advantages of examples described herein and any described disadvantages of conventional systems are not intended to be limiting, and are provided to aid in understanding. It should be understood that some examples may not exhibit all, or even any, of the described advantages. Moreover, some examples may not address all, or even any, of the described disadvantages of conventional systems.


By pairing multiple reverse osmosis (RO) vessels with a forward osmosis pre-treatment, the overall system recovery in some examples may be decoupled from the RO system recovery. Coupling of forward osmosis (FO) pre-treatment with multi-stage NF and/or RO allows for increase of overall system water recovery in some examples compared to what the recovery would be if FO pre-treatment system was not used.


An example purification system 10 according to an embodiment of the invention is illustrated in the block diagram of FIG. 1. The system 10 may be capable of treating feed solutions 100 in excess of 80,000 ppm concentration by regenerating a draw solution 105 at a concentration higher than the feed 100. While a hydrostatic pressure exceeding 1200 psi may be required in some examples to re-concentrate this draw solution with an array of RO membranes in one stage, by breaking up the re-concentration into two or more stages, each stage may operate at a hydrostatic pressure below the burst pressure of the membrane. High pressure RO elements are generally rated 1800 psi, but may be run up to 3000 psi when fouling and scaling may be mitigated.


Separating the re-concentration into multiple stages may in some examples use an intermediate pressure driven, salt rejecting membrane or membranes. While the difference in hydrostatic pressure or osmotic pressure across these membranes may not be increased with respect to the limits of a conventional RO membrane, the feed osmotic pressure may be increased by also increasing the permeate osmotic pressure, which may keep the difference in osmotic pressure between the two streams constant. A membrane with a reduced salt rejection with respect to conventional RO membranes, such as an NR membrane or loosened RO membrane, may be used.


Returning to FIG. 1, the system 10 illustrates a two-stage FO/RO system which may be capable of treating high concentration feeds to concentrations less than 120 kppm. The system may use a sodium chloride draw solute, but may be utilized with other draw solutes, in single form or in combination. The system includes three membrane arrays; an FO module 103, a low rejection pressure driven salt rejecting module 110 (LR), and an RO module 116. The FO module 103 generally includes an array of FO membranes, arranged in parallel, series, or a combination of both. Any suitable FO membrane may generally be used. The FO module 103 may generally have a high salt rejection (e.g. typically greater than 95%). The LR module 110 generally includes an array of membranes having a salt rejection less than RO (which is, for example, typically 99% or greater). The array of membranes in the LR module may be arranged in series, parallel, or a combination thereof. Generally, the module may have salt rejection (e.g. sodium chloride rejection) of less than 90%, less than 80% in some examples, less than 70% in some examples, less than 60% in some examples, less than 50% in some examples. The RO module 116 generally includes an array of RO membranes, arranged in parallel, series, or a combination of both. Any suitable RO membrane may generally be used. The RO module may have high rejection (e.g. typically greater than 99%).


During example operation, a high concentration feed stream 102, enters the FO module 103, where it is dewatered and leaves the system as reject stream 104. Generally, any stream may be used as the feed stream, including but not limited to, seawater or wastewater. A high concentration draw stream 105 (e.g., 120 kppm) flows (e.g., 1 MGD) with a pressure which may be near atmospheric enters the FO module 103, absorbing mass and becoming diluted, exiting as a first stream 106 of a reduced concentration (e.g., 80 kppm) and flows (e.g., 1.5 MGD) with a pressure which may be near atmospheric. This stream may be too high in concentration to recover with a single stage RO. The stream may then be pressurized (e.g., 1000 psi) by a pump 107, which may be a high pressure pump, then combined with an adjacent reverse osmosis reject (e.g. brine) stream 117 (which may be a high pressure stream) with a flow rate (e.g., 0.5 MGD), forming stream 109 with a flow rate (e.g., 2 MGD). The pressure may remain elevated (e.g., 1000 psi). The stream 109 may be contacted with a low rejection pressure driven salt rejecting module 110 (LR), which may have a rejection of, e.g., 50% and a recovery rate of 50%. In other examples, the salt rejection (e.g. sodium chloride rejection) of the module 110 may be less than 40%, less than 50%, less than 60%, less than 70%, less than 80%, or less than 90% in some examples. In other examples, the recovery rate of the module 110 may be less than 90%, less than 70%, less than 50%, less than 30% and greater than 10% In contrast to RO membranes where, for example, a 50% recovery results in a reject stream that is approximately twice the concentration of the feed stream limiting the recovery at high TDS, LR membranes will have a concentration less than twice the feed stream due to bulk salt transfer across the membrane, allowing for higher recovery ratios than typical RO membranes. The hydrostatic pressure of stream 109 may overcome the average difference in concentration across the membrane (e.g., 40 kppm by 300 psi), generating a low concentration stream 113 (e.g., 40 kppm) that flows (e.g., 1 MGD), and which may have a pressure near atmospheric, and a high concentration draw stream 111 (e.g. 120 kppm) which may flow (e.g., 1 MGD) and have a higher pressure (e.g., 1000 psi).


The pressure of this stream may be decreased across an energy recovery device 112 (e.g. hydraulic motor), forming a low pressure high concentration draw stream 105 that may be fed to the FO membrane array 103. A dosing pump 140 may be configured to provide a solute to the high concentration draw stream 105. The low concentration stream 113 may then be pressurized to a higher pressure (e.g., 1000 psi) by a pump 114, forming stream 115. This stream is fed to the stage 2 RO module 116 which may have a high rejection (e.g. greater than 99%, greater than 98%, greater than 97%, greater than 95%, or greater than 90% in some examples). The hydrostatic pressure may overcome the average difference in concentration across the membrane (e.g., 40 kppm by 300 psi) and may generate a high quality product stream 118.


The product stream 118 may have a concentration of nearly 0 kppm (e.g., 350 ppm), flow of 0.5 MGD and pressure near atmospheric. The RO module 116 may also produce a reverse osmosis reject stream 117 which may be combined with stream 108 and recycled as discussed above. The reverse osmosis reject stream 117 may have a concentration of 80 kppm, flow of 0.5 MOD and pressure of 1000 psi.


A nanofiltration (NF) membrane may be used as an intermediate stage 1 pressure driven salt rejecting membrane array, in module 110. Unlike RO membranes which tend to reject multivalent salts at a high percentage than monovalent salts, the NF membrane may reject monovalent salts at a higher percentage than multivalent salts. This may be leveraged by having a draw solute that includes both monovalent salts (e.g. sodium chloride or lithium chloride) and multivalent salts (e.g. magnesium chloride, calcium chloride, magnesium sulfate, or sodium phosphate). For example, a NF membrane may reject monovalent salts at 70% and multivalent salts at 30%, although other rejection percentages may be used in other examples. When entering the module 110, the multivalent salt may be more likely to leave the module in the low concentration stream 113, and the monovalent in the high concentration draw stream 111.


Consequently, the stage 2 RO module 116 may be desalting stream 115 whose salts are predominately multivalent salts, which may result in a higher quality, lower TDS product stream 118. In another example, the NF membrane may reject multivalent salts better than monovalent salts, which may result in higher specific RO flux. In other examples, the FO module 103 may receive a draw solution stream 105 whose salts are predominately monovalent salts, which may result in a higher specific flux than would be reached with multivalent salts.


Table 1 contains example flow rates, hydrostatic pressures, and concentrations of solute for different points in the system illustrated in FIG. 1. The values given in Table 1 are exemplary and should not be interpreted to limit the embodiments of the invention to the values given. Other values of flow rates, hydrostatic pressures, and concentrations of solute may be used in other examples.









TABLE 1







Exemplary Values for Two Stage FO/RO System 10












Element

Hydrostatic
Concen-



number in
Flow
pressure
tration



FIG. 1
(MGD)
(psi)
(ppm)















Feed
102
0.63
5.0
35,000


Feed Reject
104
0.13
0.0
105,000


FO draw reject
106
1.50
0.5
80,000


Pressurized FO draw
108
1.50
980
80,000


reject


Stage 1 LR draw feed
109
2.00
980
80,000


Stage 1 LR draw reject
111
1.00
965
120,000


FO draw feed
105
1.00
3.0
120,000


Stage 1 LR permeate
113
1.00
0.5
40,000


Stage 2 RO feed
115
1.00
1000
40,000


Stage 2 RO reject
117
0.50
985
80,000


System permeate
118
0.50
0.0
350










FIG. 2 illustrates a block diagram of a three stage system 20 according to an embodiment of the invention. The three stage FO RO system 20 may be capable of treating high concentration feeds to concentrations less than 160 kppm. The system is considered with a sodium chloride draw solute, but may be utilized with other draw solutes, in single form or in combination with other solutes (e.g. multivalents), including sodium chloride. The system 20 may include four membrane arrays; an FO module 103 with high rejection (e.g. typically greater than 95%), an intermediate stage 1 pressure driven salt rejecting membrane array (e.g. LR module) 125 with rejection less than RO (e.g. typically 33%), an intermediate stage 2 pressure driven salt rejecting membrane array (e.g. LR module) 132 with rejection less than RO (e.g. typically 50%) and final stage 3 RO module 137 with high rejection (e.g. typically greater than 99%).


During operation, a high concentration feed stream 102, may enter the FO module 103, where is it dewatered and leaves the system as reject or waste stream 104. A high concentration draw stream 120 (e.g. 160 kppm) flows (e.g., 1.5 MGD) with a pressure which may be near atmospheric, enters the FO module 103 absorbing mass and becoming diluted, exiting as stream 121 (e.g., 120 kppm), with increase flow (e.g., 2 MGD) with a pressure which may be near atmospheric. This stream may be too high in concentration to recover with a single or double stage RO. The stream is then pressurized to a higher pressure (e.g., 1000 psi) by a pump 122, then combined with an adjacent high pressure stream 133, forming stream 124, with an increased flow (e.g., 3 MGD) but same pressure (e.g., 1000 psi). The stream 124 is contacted with LR module 125 which may have a rejection of 33%. The hydrostatic pressure (e.g. 1000 psi) may overcome the average difference in concentration across the membrane of (e.g., 60 kppm by 300 psi), generating a low concentration stream 128 (e.g., 80 kppm) with a reduced flow (e.g., 1.5 MGD), and may have a pressure near atmospheric. The LR module 125 may also produce a high concentration draw stream 126 (e.g., 160 kppm), with a reduced flow (e.g., 1.5 MGD), and higher pressure (e.g., 1000 psi).


The pressure of stream 126 may be decreased across a hydraulic motor (energy recovery device) 127, forming stream 120 that may be fed to the FO membrane array 103. The low concentration stream 128 may then be pressurized (e.g., 1000 psi) by a second pump 129, forming stream 130. This stream 130 is then combined with an adjacent high pressure stream 138, forming stream 131, with an increased flow (e.g., 2 MGD). The stream 131 is contacted with an LR module 132 which may have a rejection of 50%. The hydrostatic pressure (e.g., 1000 psi) may overcome the average difference in concentration across the membrane (e.g., 60 kppm by 300 psi), generating a dilute stream 134 (e.g., 40 kppm), with reduced flow (e.g., 1 MGD), and may have a pressure near atmospheric, and a high concentration rejection stream 133 (e.g., 120 kppm), which may have reduced flow (e.g., 1 MGD) and higher pressure (e.g., 1000 psi). This high concentration rejection stream 133 may be combined with stream 123 as described above and recycled. The dilute stream 134 may then be pressurized (e.g., 1000 psi) by a third pump 135, forming stream 136. This stream 136 is fed to the stage 3 RO module 137, which may have a rejection greater than 99%. The hydrostatic pressure (e.g., 1000 psi) may overcome the average difference in concentration across the membrane (e.g., 60 kppm by 300 psi), generating a high quality product stream 118 which may have a concentration of nearly 0 kppm, flow of 0.5 MGD and pressure near atmospheric. The RO module 137 may also produce and a reverse osmosis reject stream 138 which may have a concentration of 80 kppm, flow of 0.5 MGD and pressure of 1000 psi. This reverse osmosis reject stream 138 may be combined with stream 130 as described above and recycled.


Table 2 contains example flow rates, hydrostatic pressures, and concentrations of solute for different points in the system illustrated in FIG. 2. The values given in Table 2 are exemplary and should not be interpreted to limit the embodiments of the invention to the values given. Other values of flow rates, hydrostatic pressures, and concentrations of solute may be possible.









TABLE 2







Exemplary Values for Three Stage FO/RO System 20












Element

Hydrostatic
Concen-



number in
Flow
pressure
tration



FIG. 2
(MGD)
(psi)
(ppm)















Feed
102
1.0
5.0
80,000


Feed Reject
104
0.55
0.0
145,000


FO draw reject
121
2.0
0.5
120,000


Pressurized FO draw
123
2.0
960
120,000


reject


Stage 1 LR draw feed
124
3.0
960
120,000


Stage 1 LR draw reject
126
1.5
945
160,000


FO draw feed
120
1.5
3.0
160,000


Stage 1 LR permeate
128
1.5
0.5
80,000


Pressurized stage 1 LR
130
1.5
980
80,000


permeate


Stage 2 LR draw feed
131
2.0
980
80,000


Stage 2 LR draw reject
133
1.0
965
120,000


Stage 2 LR permeate
134
1.0
0.5
40,000


Stage 3 RO feed
136
1.0
1000
40,000


Stage 3 RO reject
138
0.5
985
80,000


System permeate
118
0.5
0.0
350









While a two-stage system and a three-stage system have been shown in FIGS. 1 and 2, respectively, any number of stages may be used in other examples. Generally, example systems include a FO module whose draw stream output is provided to one, or a series of, LR modules having low rejection pressure driven salt rejecting membranes. Each LR module may produce a low concentration stream provided to a next LR module in the series, or to a later RO module, and a higher concentration stream fed back to a last stage (e.g. the FO module draw or to an earlier LR module). A subsequent RO module is provided which receives the low concentration stream from a last LR module in the series, providing a product stream.


The feed and draw water of examples described herein, including in systems 10 and 20, illustrated in FIGS. 1 and 2, may have additional pretreatment to remove increased concentrations of sealants or foulants at high recovery. Recovery is the ratio of the permeate stream (X) divided by the feed stream (Y). Sealants may include, but are not limited to: calcium carbonate, sodium carbonate, silica, gypsum, barium sulfate, strontium sulfate, and calcium fluoride. Foulants may include, but are not limited to: small organic molecules, particulates or colloids, or biological film growth. The feed and draw water may be treated with antiscalants or antifoulants to prevent scaling or fouling of the FO membranes or the RO membranes. Antiscalants may include condensed polyphosphates, organophosphonates, and polyelectrolytes. Dechlorination of the feed water may be achieved by the addition of sodium bisulfite. The pH of feed water and the draw may be raised to remove hardness and alkalinity or increase rejection of weakly ionized anions, such as borate, cyanide, fluoride, and certain arsenic and selenium compounds. The pH of feed water and the draw may be lowered to reduce scaling. Either the feed or the draw may have additional antiscalants, antifoulants, pH adjustments, degassing, in any combination and in any order, depending on the feed water, the operation parameters (e.g., recovery ratio), and the desired system permeate quality.


The sealant and foulant removal process of the draw stream, such as pH adjustments, may be completed in batch mode where the draw loop is drained and replaced with another draw solution while the sealant and foulant removal process is completed. The sealant and foulant removal process may also be completed in semi-batch mode, such that a small portion of the draw loop is removed for treatment at a time. The rejection and the scaling and fouling propensity of the forward osmosis membrane and the reverse osmosis membrane may be independently adjusted. The system may then be optimized to minimize consumables and maximize overall efficiency as desired for a specific application.


Unlike traditional reverse osmosis systems, the draw solution composition of the FO/RO systems shown in FIGS. 1 and 2 may be tuned to optimize the performance of the system. The draw solution may be any aqueous solution with high rejection from a reverse osmosis membrane. The draw solute may preferably be an inorganic salt such as sodium chloride, magnesium chloride, magnesium sulfate, sodium sulfate, or sodium phosphate. The draw solute may be monovalent or multivalent. The draw solution may be a mixture of salts, both monovalent or multivalent. The low rejection reverse osmosis membrane, such as those included in the LR modules, may be a standard reverse osmosis membrane for high sodium chloride rejection (e.g. greater than 99%), such as DOW SW30 membrane. The low rejection reverse osmosis membrane may be a nanofiltration membrane, such as DOW NF90, with moderate sodium chloride rejection (greater than 80%) and high multivalent rejection (e.g. greater than 90%). The low rejection reverse osmosis membrane may be a sulfonated polysulfone nanofiltration membrane, such as Hydranautics HydraCoRe70.


In both systems illustrated in FIGS. 1 and 2, the low rejection reverse osmosis membrane, which may be included in the LR modules, may be tuned by chemically treating a standard reverse osmosis membrane. In some examples, the low rejection reverse osmosis membrane may be a thin film composite membrane with a polyamide selective layer. The crosslinking density of the polyamide layer may be reduced, increasing salt passage (reducing selectivity) and increasing water permeability. For example, a DOW SW30 membrane may be exposed to 1000 ppm sodium hypochlorite solution for 10 minutes to 6 hours and then rinsed with sodium bisulfate or water. The sodium chloride rejection of the membrane may be reduced from 99% to 10%. The treated membrane may have high multivalent salt rejection. The draw solute composition of monovalent and multivalent salts and the reverse osmosis membrane may be chosen depending on the relative rejection of the membrane to monovalent salts and multivalent salts and the preferred operation parameters.


A multi-port purification system 30 according to the principles of the present invention is illustrated in FIG. 3. In this example, a draw solution 300 is brought to a first port 310 of a first RO element 315 by pump 305. A reject stream 355 from the first RO element 315 is depressurized and returned by energy recovery device 370 to the draw solution as a concentrated stream 360. The permeate 320 is pressurized by pump 325 and delivered to an input port 330 in a second RO element 335. Product leaves the RO element 335 as stream 340. A reject stream 345 is depressurized by an energy recovery device 365 and returned to a second port 350 in the first RO element 315.


In the example embodiment shown in FIG. 3, osmotic pre-treatment may be used with multiple RO stages and a 4-port RO element. The 4-port RO element may allow a saline solution to circulate through the permeate channel of RO1, which may decrease the effective osmotic pressure differential across the membrane RO1. Vessel RO2 may utilize a standard 3-port RO element. The concentration of the intermediate draw solution may be between the inlet draw solution concentration and the product water. In a two stage system, this concentration may be about half of the difference between the inlet draw solution and product water concentrations. In this example, the salinity difference across each RO element may be only about half of the total reduction in salinity from inlet to product.


The water recovery of this multi-stage RO system alone without FO pre-treatment is the product of water recoveries of each of the RO steps. For a system where water recovery of each of the RO steps is 10%, the overall system water recovery is only 1%. However, when an FO pre-treatment system is coupled to a multi-stage RO system, the overall recovery of the whole system is equal to the water recovery of the FO loop and independent of the water-recovery of the RO portion of the system, thus it can be greater than 1%.


From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention.

Claims
  • 1. A system, comprising: a system output;a plurality of low rejection stages connected in series, wherein a first low rejection stage of the plurality of low rejection stages is configured to receive a first stream from a draw side of a forward osmosis stage fluidly coupled thereto and provide a first output stream to the next low rejection stage in the plurality of low rejection stages, wherein the plurality of low rejection membrane stages include low rejection membrane modules having a low rejection membrane with a salt rejection rate of less than 90% at a first hydrostatic pressure, wherein the plurality of low rejection stages further comprises a final low rejection stage subsequent to the first low rejection stage, wherein the final low rejection stage is configured to provide a second output stream and a final reject stream, wherein the final reject stream is fluidly coupled to the first stream and provided to the draw side of the forward osmosis stage;a reverse osmosis stage configured to receive the second output stream from the final low rejection stage of the plurality of low rejection stages, wherein the reverse osmosis stage is further configured to provide a product stream and a reverse osmosis reject stream, wherein the reverse osmosis stage has a reverse osmosis membrane with a higher salt rejection than the low rejection membrane modules at the first hydrostatic pressure, wherein the product stream is provided to the system output as water;wherein the reverse osmosis reject stream is fluidly coupled to the first output stream directly prior to the final low rejection stage to recycle the reverse osmosis reject stream through the system, wherein at least a portion of the reverse osmosis reject stream is fluidly coupled with the first stream and provided to the draw side of the forward osmosis stage.
  • 2. The system of claim 1, wherein the plurality of low rejection stages are configured to provide the final reject stream to a previous low rejection stage of the plurality of low rejection stages connected in series.
  • 3. The system of claim 1, wherein a recovery rate of the plurality of low rejection stages is less than 90%.
  • 4. The system of claim 1, wherein at least one of the plurality of low rejection stages has a salt rejection of less than 80% at the first hydrostatic pressure.
  • 5. The system of claim 1, further comprising a pump configured to pressurize the first stream.
  • 6. The system of claim 5, wherein the pump is configured to pressurize the first stream to a hydrostatic pressure of less than 3000 psi.
  • 7. The system of claim 1, further comprising a pump configured to receive the second output stream from the final low rejection stage of the plurality of low rejection stages and pressurize the second output stream prior to the reverse osmosis stage.
  • 8. The system of claim 1, further comprising an energy recovery device configured to receive a high pressure reject stream from one or more of the plurality of low rejection stages and to reduce the pressure of the high pressure reject stream.
  • 9. The system of claim 1, wherein the portion of the reverse osmosis reject stream is operably coupled to the first stream prior to the plurality of low rejection membrane stages.
  • 10. The system of claim 1, wherein the reverse osmosis stage is further configured to directly provide the product stream to the system output.
  • 11. A system, comprising: a first pump configured to pressurize a first stream;a plurality of low rejection stages connected in series, wherein a first low rejection stage of the plurality of low rejection stages is configured to receive the pressurized first stream from a draw side of a forward osmosis stage fluidly coupled thereto and provide a first output stream to the next low rejection stage in the plurality of low rejection stages, wherein the plurality of low rejection membrane stages include low rejection membrane modules having a low rejection membrane with a salt rejection rate of less than 90% at a first hydrostatic pressure, wherein the final low rejection stage is configured to provide a second output stream and a final reject stream, wherein the final reject stream is fluidly coupled to the pressurized first stream and provided to the draw side of the forward osmosis stage;a second pump configured to receive the second output stream from the final low rejection stage of the plurality of low rejection stages and pressurize the second output stream, wherein the final low rejection stage is subsequent to the first low rejection stage;a system output; anda reverse osmosis stage configured to receive the pressurized second output stream from the final low rejection stage, wherein the reverse osmosis stage is further configured to provide a product stream and a reverse osmosis reject stream, wherein the reverse osmosis stage has a reverse osmosis membrane with a higher salt rejection than the low rejection membrane modules at the first hydrostatic pressure, wherein the product stream is provided to the system output as water;wherein at least a portion of the reverse osmosis reject stream is fluidly coupled to the first stream directly prior to the final low rejection stage to recycle the reverse osmosis reject stream and provided to the draw side of the forward osmosis stage.
  • 12. The system of claim 11, wherein the reverse osmosis stage is further configured to directly provide the product stream to the system output.
  • 13. The system of claim 12, wherein the draw side includes a diluted draw stream output of the forward osmosis stage and the diluted draw stream output is fluidly coupled to the first low rejection stage of the plurality of low rejection stages.
  • 14. The system of claim 12, further comprising an energy recovery device configured to receive a high pressure reject stream from one or more of the plurality of low rejection stages and to reduce the pressure of the high pressure reject stream.
CROSS-REFERENCE

This application is a divisional of U.S. application Ser. No. 14/777,418 filed Sep. 15, 2015, which is a 371 National Stage application claiming priority to PCT Application No. PCT/US2014/029332 filed Mar. 14, 2014, which application claims the benefit of the earlier filing date of U.S. Provisional Application No. 61/794,537 filed Mar. 15, 2013, which applications are incorporated herein by reference, in their entirety, for any purposes.

GOVERNMENT SPONSORSHIP

This invention was made with Government support under contract number W911NF-09-C-0079 awarded by the Department of Defense. The Government has certain rights in this invention.

US Referenced Citations (170)
Number Name Date Kind
2116920 Wickenden May 1938 A
3216930 Glew Nov 1965 A
3352422 Heden Nov 1967 A
3721621 Hough Mar 1973 A
4326509 Usukura Apr 1982 A
4428720 Van Erden et al. Jan 1984 A
4454176 Buckfelder et al. Jun 1984 A
4618533 Steuck Oct 1986 A
4756835 Wilson Jul 1988 A
4792402 Fricker Dec 1988 A
4900443 Wrasidlo Feb 1990 A
4959237 Walker Sep 1990 A
5084220 Moller Jan 1992 A
5100556 Nichols Mar 1992 A
5192434 Moller Mar 1993 A
5238574 Kawashima et al. Aug 1993 A
5281430 Herron et al. Jan 1994 A
5593738 Ihm et al. Jan 1997 A
5635071 Al-Samadi Jun 1997 A
6261879 Houston et al. Jul 2001 B1
6406626 Murakami et al. Jun 2002 B1
6413070 Meyering et al. Jul 2002 B1
6513666 Meyering et al. Feb 2003 B2
6755970 Knappe et al. Jun 2004 B1
6849184 Lampi et al. Feb 2005 B1
6884375 Wang et al. Apr 2005 B2
6992051 Anderson Jan 2006 B2
7177978 Kanekar et al. Feb 2007 B2
7205069 Smalley et al. Apr 2007 B2
7445712 Herron Nov 2008 B2
7611628 Hinds, III Nov 2009 B1
7627938 Kim et al. Dec 2009 B2
7799221 MacHarg Sep 2010 B1
7879243 Al-Mayahi et al. Feb 2011 B2
7901578 Pruet Mar 2011 B2
7955506 Bryan et al. Jun 2011 B2
8029671 Cath et al. Oct 2011 B2
8029857 Hoek et al. Oct 2011 B2
8038887 Bakajin et al. Oct 2011 B2
8083942 Cath et al. Dec 2011 B2
8177978 Kurth et al. May 2012 B2
8181794 Mcginnis et al. May 2012 B2
8221629 Al-Mayahi et al. Jul 2012 B2
8246791 McGinnis et al. Aug 2012 B2
8252350 Cadwalader et al. Aug 2012 B1
8356717 Waller, Jr. et al. Jan 2013 B2
8518276 Stiemer et al. Aug 2013 B2
8567612 Kurth et al. Oct 2013 B2
8920654 Revanur et al. Dec 2014 B2
8960449 Tomioka et al. Feb 2015 B2
9216391 Revanur et al. Dec 2015 B2
9227360 Lulevich et al. Jan 2016 B2
9636635 Benton et al. May 2017 B2
9861937 Benton et al. Jan 2018 B2
11090611 Benton et al. Aug 2021 B2
20010006158 Ho et al. Jul 2001 A1
20020063093 Rice et al. May 2002 A1
20020148769 Deuschle et al. Oct 2002 A1
20030038074 Patil Feb 2003 A1
20030141250 Kihara Jul 2003 A1
20030173285 Schmidt et al. Sep 2003 A1
20030205526 Vuong Nov 2003 A1
20040004037 Herron Jan 2004 A1
20040071951 Jin Apr 2004 A1
20040084364 Kools May 2004 A1
20050016922 Enzweiler Jan 2005 A1
20050056590 Baggott et al. Mar 2005 A1
20050142385 Jin Jun 2005 A1
20050166978 Brueckmann et al. Aug 2005 A1
20060144789 Cath Jul 2006 A1
20060233694 Sandhu et al. Oct 2006 A1
20070181473 Manth et al. Aug 2007 A1
20070215544 Kando et al. Sep 2007 A1
20070246426 Collins Oct 2007 A1
20080017578 Childs et al. Jan 2008 A1
20080149561 Chu et al. Jun 2008 A1
20080210370 Smalley et al. Sep 2008 A1
20080223795 Bakajin et al. Sep 2008 A1
20080236804 Cola et al. Oct 2008 A1
20080237126 Hoek et al. Oct 2008 A1
20080290020 Marand et al. Nov 2008 A1
20090078640 Chu et al. Mar 2009 A1
20090214847 Maruyama et al. Aug 2009 A1
20090250392 Thorsen et al. Oct 2009 A1
20090272692 Kurth et al. Nov 2009 A1
20090283475 Hylton et al. Nov 2009 A1
20090308727 Kirts Dec 2009 A1
20090321355 Ratto et al. Dec 2009 A1
20100018921 Ruehr et al. Jan 2010 A1
20100025330 Ratto et al. Feb 2010 A1
20100032377 Wohlert Feb 2010 A1
20100051538 Freeman et al. Mar 2010 A1
20100059433 Freeman et al. Mar 2010 A1
20100062156 Kurth et al. Mar 2010 A1
20100140162 Jangbarwala Jun 2010 A1
20100155333 Husain et al. Jun 2010 A1
20100192575 Al-Mayahi Aug 2010 A1
20100206743 Sharif et al. Aug 2010 A1
20100206811 Ng et al. Aug 2010 A1
20100212319 Donovan Aug 2010 A1
20100224550 Herron Sep 2010 A1
20100224561 Marcin Sep 2010 A1
20100297429 Wang et al. Nov 2010 A1
20100320140 Nowak et al. Dec 2010 A1
20100326833 Messalem et al. Dec 2010 A1
20110017666 Cath et al. Jan 2011 A1
20110036774 McGinnis Feb 2011 A1
20110057322 Matsunaga et al. Mar 2011 A1
20110073540 McGinnis et al. Mar 2011 A1
20110132834 Tomioka et al. Jun 2011 A1
20110133487 Oklejas, Jr. Jun 2011 A1
20110155666 Prakash Jun 2011 A1
20110186506 Ratto et al. Aug 2011 A1
20110198285 Wallace Aug 2011 A1
20110203994 Mcginnis et al. Aug 2011 A1
20110220574 Bakajin et al. Sep 2011 A1
20110284456 Brozell et al. Nov 2011 A1
20110311427 Hauge et al. Dec 2011 A1
20120008038 Yen et al. Jan 2012 A1
20120012511 Kim et al. Jan 2012 A1
20120043274 Chi et al. Feb 2012 A1
20120080378 Revanur et al. Apr 2012 A1
20120080381 Wang et al. Apr 2012 A1
20120103892 Beauchamp et al. May 2012 A1
20120118743 Liang et al. May 2012 A1
20120118826 Liberman et al. May 2012 A1
20120118827 Chang et al. May 2012 A1
20120132595 Bornia May 2012 A1
20120152841 Vissing et al. Jun 2012 A1
20120160753 Vora et al. Jun 2012 A1
20120231535 Herron et al. Sep 2012 A1
20120234758 McGinnis et al. Sep 2012 A1
20120241371 Revanur et al. Sep 2012 A1
20120241373 Na et al. Sep 2012 A1
20120251521 Rostro et al. Oct 2012 A1
20120261321 Han et al. Oct 2012 A1
20120267297 Iyer Oct 2012 A1
20120267306 McGinnis et al. Oct 2012 A1
20120273421 Perry et al. Nov 2012 A1
20120298381 Taylor Nov 2012 A1
20130001162 Yangali-Quintanilla et al. Jan 2013 A1
20130095241 Lulevich et al. Apr 2013 A1
20130105383 Tang et al. May 2013 A1
20130126431 Henson et al. May 2013 A1
20130203873 Linder et al. Aug 2013 A1
20130220581 Herron et al. Aug 2013 A1
20130220927 Moody et al. Aug 2013 A1
20130264285 Macintosh Oct 2013 A1
20140015159 Lazar et al. Jan 2014 A1
20140175011 Benton et al. Jun 2014 A1
20140302579 Boulanger et al. Oct 2014 A1
20140319056 Fuchigami et al. Oct 2014 A1
20150014232 McGinnis et al. Jan 2015 A1
20150014248 Herron et al. Jan 2015 A1
20150064306 Tatera et al. Mar 2015 A1
20150273399 Roh et al. Oct 2015 A1
20160002074 Benton et al. Jan 2016 A1
20160038880 Benton et al. Feb 2016 A1
20160136577 McGovern et al. May 2016 A1
20160136578 McGovern et al. May 2016 A1
20160136579 McGovern et al. May 2016 A1
20160230133 Peterson et al. Aug 2016 A1
20170121190 Ikuno May 2017 A1
20170190650 Peterson et al. Jul 2017 A1
20170197181 Benton et al. Jul 2017 A1
20170232392 Desormeaux et al. Aug 2017 A1
20170333847 Lulevich et al. Nov 2017 A1
20180311618 Benton et al. Nov 2018 A1
20200094193 Benton et al. Mar 2020 A1
20210339201 Benton et al. Nov 2021 A1
Foreign Referenced Citations (55)
Number Date Country
2785807 Jul 2011 CA
101228214 Jul 2008 CN
102642894 Aug 2012 CN
102674605 Sep 2012 CN
1894612 Mar 2008 EP
3181215 Jun 2017 EP
2189091 Jan 1974 FR
S55149682 Nov 1980 JP
59059213 Apr 1984 JP
S5959213 Apr 1984 JP
62-140620 Jun 1987 JP
2005-138028 Jun 2005 JP
2010094641 Apr 2010 JP
2012183492 Sep 2012 JP
2013081922 May 2013 JP
2013128874 Jul 2013 JP
101144316 May 2012 KR
101229482 Feb 2013 KR
1993010889 Jun 1993 WO
9962623 Dec 1999 WO
0213955 Feb 2002 WO
2006040175 Apr 2006 WO
2008137082 Nov 2008 WO
2009035415 Mar 2009 WO
2009039467 Mar 2009 WO
WO2010002165 Jun 2009 WO
2009104214 Aug 2009 WO
2009129354 Oct 2009 WO
2009129354 Oct 2009 WO
2010006196 Jan 2010 WO
2010050421 May 2010 WO
2010067063 Jun 2010 WO
2010067065 Jun 2010 WO
2010144057 Dec 2010 WO
2011028541 Mar 2011 WO
2011028541 Mar 2011 WO
2012047282 Apr 2012 WO
2012084960 Jun 2012 WO
2012095506 Jul 2012 WO
2012102677 Aug 2012 WO
2012135065 Oct 2012 WO
2013022945 Feb 2013 WO
2013032742 Mar 2013 WO
2013059314 Apr 2013 WO
2014063149 Apr 2014 WO
2014071238 May 2014 WO
2014100766 Jun 2014 WO
2014144704 Sep 2014 WO
2014144778 Sep 2014 WO
WO2014144778 Sep 2014 WO
2016022954 Feb 2016 WO
2016070103 May 2016 WO
2016210337 Dec 2016 WO
2016210337 Dec 2016 WO
2018119460 Jun 2018 WO
Non-Patent Literature Citations (51)
Entry
English language machine translation of WO2010002165, 12 Pages, No Date.
U.S. Appl. No. 17/375,932 titled “Separation Systems, Elements, and Methods for Separation Utilizing Stacked Membranes and Spacers” filed Jul. 14, 2021.
English translation of Office Action for CN Application No. 201680045242.X, dated Sep. 2, 2021.
Summons to Attend Oral Proceedings for EP 16815432.6, mailed Jul. 9, 2021.
Shon, Ho K. et al., “Introduction: Role of Membrane Science and Technology And Forward Osmosis Processes”, https://app.knovel.com/hotlink/toc/id:kpFOFA0001/forward-osmosis-fundamentals/forward-osmosis-fundamentals, 2015, pp. 1, 5-6.
English translation of Office Action for BR Application No. 1120150147763, dated Apr. 8, 2021.
English translation of Office Action for CN Application No. 201680045242, dated Apr. 8, 2021.
English translation of Office Action for CN Application No. 201680045242.X, dated Jul. 15, 2020.
Office Action dated Jul. 27, 2020 for EP Application No. 13865011.4.
Office Action for AU Application No. 2016283127, dated Nov. 20, 2020.
Office Action for EP Application No. 14764413.2, dated Mar. 9, 2021.
“Guide To Forward Osmosis Membranes”, ForwardOsmosisTech, https://www.forwardosmosistech.com/forward-osmosis-membranes/ (last visited Aug. 19, 2020).
“Osmotic Pressure and Solutions”, Center for Student Success and Academic Counseling, The University of North Carolina at Chapel Hill, http://cssac.unc.edu/programs/learning-center/Resources/Study/Guides/Chemistry%20102/Osmotic%20Pressure, accessed Jan. 20, 2021.
English Translation of Final Rejection for CN Application No. 201480022732.9 dated Jun. 26, 2018.
Examination Report No. 2 dated Apr. 6, 2018 for Australian application No. 2014228787, 3 pages.
Extended European Seatch Report received for EP Appl. No. 14764413.2 dated Feb. 8, 2017.
Fourth OA for CN Application No. 201480022732.9, dated Dec. 28, 2017.
International Search Report and Written Opinion for app. No. PCT/US2014/029332 dated Jul. 3, 2014.
Third OA for CN Application No. 201480022732.9, dated Jun. 29, 2017.
U.S. Appl. No. 16/473,088 titled “Methods of Dewatering of Alcoholic Solutions via Forward Osmosis and Related Systems” filed Dec. 22, 2017.
“Examination Report No. 1 dated May 15, 2017 for Australian application No. 2014228787, 4 pages.”
“Extended European Seatch Report receivedfor EP Appl. No. 14764413.2 dated Jan. 2, 2017”.
“First Office Action for PRC (China) Pat. Appln. No. 201480022732.9 dated Jul. 5, 2016”.
“Second Office Action for PRC (China) Pat. Appln. No. 201480022732.9 dated Jan. 16, 2017”.
Akthakul, et al., “Antifouling polymer membranes with subnanometer size selectivity”, Macromolecules 37, Sep. 3, 2004, 7663-7668.
Beibei, et al., “(Category A—No Translation—do not cite per client) Preparation of Thin Film Composite Membrane by Interfacial Polymerization Method”, Progress in Chemistry, vol. 19, No. 9, Sep. 30, 2007, 1-8.
Blandin, et al., “Validation of assisted forward osmosis (AFO) process: Impact of hydraulic pressure”, Journal of Membrane Science vol. 447, pp. 1-11, Jun. 2013.
Cath, et al., “Forward osmosis: principles, applications and recent developments”, Journal of Membrane Science 281, May 31, 2006, 70-87.
Chen, et al., Influences of molecular weight, molecular size, flux, and recovery for aromatic pesticide removal by nanofiltration membranes, Jan. 2004, Desalination 160, pp. 103-111.
Ju, et al., “Effect of monomer structure on separation property of polyamides composite membrane”, Macromolecule Transactions, No. 2, Apr. 30, 2006.
Li, et al., “Electronic properties of multiwalled carbon nanotubes in an embedded vertical array”, Applied Physics Letters vol. 81, No. 5, Jul. 2002, 910-912.
Mandal, et al., “Drug delivery system based on chronobiology—a review”, Journal of Controlled Release 147, Aug. 4, 2010, 314-325.
Mccutcheon, et al., “Influence of membrane support layer hydrophobicity on water flux in osmotically driven membrane processes”, Journal of Membrane Science, Mar. 2008, 458-466.
Mceuen, P. et al., “Single-Walled Nanotubes Electronics”, IEEE Transactions on Nanotechnology, Vo.1, No. 1, Mar. 2002.
Santus, et al., “Osmotic drug delivery: a review of the patent literature”, Journal of Controlled Release 35, Jul. 1995, 1-21.
Sotthivirat, et al., “Controlled porosity-osmotic pump pellets of a poorly water-soluble drug using sulfobutylether-b-cyclodestrin, (SBE)_7M-b-CD, as a solubilizing and osmotic agent”, Journal of Pharmaceutical Sciences vol. 96, No. 9, Sep. 2007, 2364-2374.
Yip, et al., “High Performance Thin-Film Composite Forward Osmosis Membrane”, Environmental Science and Technology, Apr. 21, 2010, 3812-3818.
Yip, et al., “High performance Thin-Film Composite Forward Osmosis Membrane”, Environmental Science andTechnology vol. 44, Apr. 21, 2010, 3812-3818.
Yip, Nagai Y. et al., “High Performance Thin-Film Composite Forward Osmosis Membrane”, Environmental Science & Technology, vol. 44, No. 10, 2010, Apr. 21, 2010, 3812-3818.
Zhao, et al., “Modification of porous poly (vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase inversion process”, Journal of Membrane Science 310, Mar. 2008, 567-576.
PCT Application PCT/US21/50330 titled “Methods and Systems for Concentrating Acetic Acid Solutions with a Multi-Tier, Ultrahigh Pressure Reverse Osmosis” filed Sep. 14, 2021.
“Hydranautics—A Nitto Group Company, “Pro Series—Specialty Membrane Products for Challenging Industrial Wastewaters””, Pro-Series-Brochure (published online: May 18, 2020); pp. 1-4 (p. 2, col. 2, paragraph 2); URL: https://membranes.com/wp-content/uploads/Documents/brochure/PRO/PRO-Series-Brochure_web.pdf, May 18, 2020.
“International Search Report and Written Opinion for PCT/US2021/050330, dated Dec. 29, 2021”.
Low , et al., “Challenges in membrane-based liquid phase separations”, Green Chemical Engineering, vol. 2, Issue 1 (Mar. 2021), pp. 3-13.
English Translation of Office Action dated Jul. 13, 2022 for CL Appl. No. 3297-2017.
Examination Report for AU Patent App. No. 2021204374, dated Apr. 21, 2022.
“Examination Report for EP 13865011.4, dated Dec. 6, 2022”.
Summany of Office Action dated Jul. 8, 2019, for CL3297-2017.
“Notice of Hearing for IN Appl. No. 2023/KOLNP/2015, mailed on Dec. 20, 2022”.
U.S. Appl. No. 18/165,162 titled, “Methods of Dewatering of Alcoholic Solutions Via Forward Osmosis Andrelated Systems,” filed Feb. 6, 2023.
U.S. Appl. No. 18/245,356, filed Mar. 15, 2023 titled, “Methods and Systems for Concentrating Acetic Acid Solutions With a Multi-Tier, Ultra-High Pressure Reverse Osmosis.”
Related Publications (1)
Number Date Country
20200086274 A1 Mar 2020 US
Provisional Applications (1)
Number Date Country
61794537 Mar 2013 US
Divisions (1)
Number Date Country
Parent 14777418 US
Child 16684406 US