WO 2018/048735 discloses a device operative in separating particles in a flowing suspension of the particles in a liquid which device comprises: a first, pressurized cavity or plenum adapted to contain a gas, separated by a first gas permeable wall from a second cavity or plenum which contains a charged particle containing liquid which also contains an ion species formed by the dissolution of the gas within the liquid, which is in turn separated by a second permeable wall from the ambient atmosphere or an optional, third, relatively reduced pressure cavity or plenum which may contain a gas or a vacuum; wherein: the permeable walls operate to permit for the transfer of a gas from the first cavity through the second cavity and through the second permeable wall to the atmosphere or a third cavity and, the pressure present in atmosphere or the third cavity is lesser than that of the first cavity, thus forming an ion concentration differential within the liquid and between the permeable walls.
The related article “Membraneless water filtration using CO2” by Shin et al. (Nature Communications 8:15181), 2 May 2017, describes a continuous flow particle filtration device in which a colloidal suspension flows through a straight channel in a gas permeable material made of polydimethylsiloxane (PDMS). A CO2 (carbon dioxide) gas channel passes parallel to the wall and dissolves into the flow stream. An air channel on the other side of the wall prevents saturation of CO2 in the suspension and the resulting gradient of CO2 causes particles to concentrate on sides of the channel, with negatively charged particles moving toward the air channel and positively charged particles toward the CO2 channel. The water away from the sides of the channel can be collected as filtered water.
The article “Diffusiophoresis at the macroscale” by Mauger et al. (arXiv: 1512.05005v4), 6 Jul. 2016, discloses that solute concentration gradients caused by salts such as LiCl impact colloidal transport at lengthscales ranging roughly from the centimeter down to the smallest scales resolved by the article. Colloids of a diameter of 200 nm were examined.
The article “Origins of concentration gradients for diffusiophoresis” by Velegol et al, (10.1039/c6sm00052e), 13 May 2016, describes diffusiophoresis possibly occurring in georeservoir extractions, physiological systems, drying operations, laboratory and industrial separations, crystallization operations, membrane processes, and many other situations, often without being recognized.
PCT Publication WO 2015/077674 discloses a process that places a microparticle including a salt in proximity to a membrane such that the microparticle creates a gradient generated spontaneous electric field or a gradient generated spontaneous chemiphoretic field in the solvent proximal to the membrane. This gradient actively draws charged particles, via diffusiophoresis, away from the membrane thereby removing charged particulate matter away from the membrane or preventing its deposition.
U.S. Pat. No. 10,463,994 and PCT Publication No. WO 2019/099586 of the present applicant describe diffusiophoretic water filtration devices and both are incorporated in their entirety herein.
For gas-driven diffusiophoretic water filters, one of the most difficult challenges has been simplifying the inlet and outlet structures, as well as the filter structure to provide for easily scalable and cost-effective diffusiophoretic water filtration.
The present applicant has developed a gas-driven diffusiophoretic water filter (DWF) that addressed almost all the of the problems faced until now, and simplifies the inlet and outlet structures and manufacturing difficulties found in the devices described in WO 2018/048735.
The present invention advantageously provides an easily manufactured and assembled, cost-effective and scalable diffusiophoretic water filtration system that is less prone to clogging and easier to operate than prior art devices.
The present invention first provides for a simplified inlet structure that allows placement of the DWF directly in a reservoir or with another type of simple manifold structure, such as a tube with a longitudinal slit.
The present invention thus provides a diffusiophoretic water filter with a membrane having a first side and an opposing second side, at least one membrane having a plurality of diffusiophoretic water channels in the first side between a first free end and a second free end of the membrane, the diffusiophoretic water channels having inlets at the first free end.
By having the inlets at a free end of the membrane, the free end can be placed in a reservoir or covered by a tube without regard to placement of the membrane or the size of the reservoir or tube, and allows for easy sealing of the inlet and setting of flow velocity for example by a water height or pressure in an easy manner.
The first free end preferably has a first edge that is perpendicular to the first side, the inlets being cut into the free end at the first edge.
The at least membrane preferably includes two membranes sandwiched together to define the channels, and most preferably the two membranes are of similar structure facing each other so that each of the membranes defines half of a height of the channel.
This construction then allows for easier implementation of a second key aspect of the present invention, which is a simplified outlet structure.
The present invention also provides a DWF with a membrane having a first side and an opposing second side, at least one membrane having a plurality of diffusiophoretic water channels in the first side between a first free end and a second free end of the membrane, the diffusiophoretic water channels having an outlet at the second free end. An outlet splitter extends into the second free end and contacts the at least one membrane to split the diffusiophoretic water channels into a clean water stream and a waste water stream.
By having a separate outlet splitter extend into the second free end, the at least one membrane may be manufactured separately and easily and cost-effectively, and also the clean water may be collected more effectively from the second free end and waste water discarded or reused more effectively.
The second free end preferably has a second edge that is perpendicular to the first side, the inlets being cut into the second free end at the second edge.
The at least membrane preferably includes two membranes sandwiched together to define the channels, and most preferably the two membranes are of similar structure facing each other so that each of the membranes defines half of a height of the channel.
The use of membranes with a plurality of diffusiophoretic water channels in the first side between a first free end and a second free end of the membrane also allows for advantageous methods of manufacture and low-cost devices.
In a first method, a roll of gas-permeable material such as PDMS can be unrolled from a roll, and moved in a longitudinal direction, the channels at least partly manufactured into the material by a plurality of lasers extending transverse to the longitudinal direction. The material can then be cut transversely to form the membrane.
The lasers preferably are stationary.
Advantageously, in one embodiment the membrane has a half channel with a half thickness so that the membranes can be sandwiched together around a splitter to form a 50/50 split. However, other than 50/50 splits are possible if one membrane has for example 70% of a channel thickness and another membrane has 30% of the thickness.
In a second embodiment the channels are manufactured at full thickness on one membrane and an unstructured or flat membrane can top the membrane with the channels. In this embodiment the splitter is not sandwiched between two membranes but can be stuck into the second edge of the structured membrane, for example as a steel blade entering a PDMS material, or manufactured by at least one laser into the second edge of the structured membrane.
The edge laser preferably is more precise and of higher quality, such as an Nd:YAG laser than the channel lasers, which may be for example inexpensive CO2 lasers, to permit thin splitters.
In the first method, the structured membrane can be re-rolled and then cut to length as desired, a length of the cut material defining length of the channels in a DWF. The width of the roll can define the width of the DWF.
In a second method, the roll of gas-permeable material is unrolled from a roll and moved in longitudinal direction, preferably stopped, and then an array of channel lasers extending in the longitudinal direction is moved transverse to the longitudinal direction. The array of channel lasers can extend for several meters or tens of meters or more and includes thousands or tens of thousands or more of inexpensive lasers for manufacturing the channels. The material can then be rolled up again and transported easily. Kilometers of inexpensive gas-permeable material can be inexpensively manufactured, and cut to length when desired, the cut length then defining the width of the membrane in a DWF.
Preferably, the width of the roll in the second method is the same as a desired length of the channels, for example between 30 cm and a meter, and each edge of the roll defines the first and second ends of the membranes. In this way the roll need not be split longitudinally. The width thus defines the dwell time of water in the channels.
In either the first or the second method, the gas permeable material may advantageously have a first flat side into which the channels are manufactured, and a second ribbed side, for example with 1 mm spaced ribs transverse to the unrolling direction. The ribs can be made by lasers or during manufacture of the membrane. The channels preferably are manufactured on the flat side opposite the space between the ribs. In this way, the channels are on narrower membrane material, and the spacing between the ribs can permit both CO2 or other gas to reach the channels, and also allow the opposite side of the channels to face atmosphere or another area with a lower concentration than the gas creating diffusiophoretic action.
The ribs also advantageously can be used to keep the membrane taut at the channels and also to permit the membrane to be supported by a support, preferably of a more rigid material.
In one embodiment, the present invention thus provides a gas-driven diffusiophoretic filter with a first membrane support having a longitudinally-extending first hollow interior; a gas-permeable first membrane covering the first hollow interior. A second membrane support can support a gas-permeable second membrane, the first and second supports being positionable so that the first and second membrane define at least one diffusiophoretic water channel.
Advantageous further optional features of the invention include one or more of the following, alone or in combination:
the first and/or second membranes have two longitudinally-extending side walls between a channel base, for example each having a 120 micrometer thick PDMS side wall approximately 0.5 cm wide, with a membrane base having a thickness of 30 micrometers extending 1.5 cm widthwide between the side walls;
longitudinally extending support ridges extend from the membrane base to match the side wall thickness and aid in preventing bulging, this the 1.5 cm wide channel may for example have two ridges each 0.3 cm wide and extending out 120 micrometers evenly spaced so that three 0.3 cm wide longitudinal flow half-channels are defined. Many more ridges and narrower channels, as well as thinner or thicker half-channels can be provided, with a thickness of a total channel preferably being less than 1 mm and thus of a half channel being 500 micrometers;
the side walls and membrane base are manufactured together, preferably by soft lithography of a PDMS or other gas-permeable material. The simple channel structure allows for inexpensive and simple lithography masks, for example of a membrane with a one to ten half-channels 120 micrometers thick into a 150 micrometer thick PDMS material;
the first and second membranes are identical, so that the side walls and any ridges align when contacted together so that the two half-channels define a full channel, advantageously easing manufacture, so that a single mask for example can be used to create a channel structure;
in an alternate embodiment the first and second membranes are simply sheets of unstructured gas-permeable material, such as PDMS 30 micrometers thick, and a separate channel structure made for example of tapes is laid over the membranes;
the first and second support structures are identical, and made of plastic, most preferably PVC and have a length between 30 and 170 cm, more preferably between 50 and 150 cm, and most preferably between 60 and 120 cm, which allows for excellent handling and easy assembling of the filter by hand, as will be described, while still allow for long dwell timed for diffusiophoretic action. In a preferred embodiment the first and second support structures are 80 cm in length;
the first and second supports each have a U-shaped cross-sectional wall structure with top edges of the wall structure being a similar width, within 25%, more preferably 10% and most preferably the same, as the membrane side wall width. This provides excellent support for the membrane on the support. The walls of the support structures thus may be 50 mm wide for example, extending from a 2.5 cm side base, so that the hollow interior is 1.5 cm wide. Inwardly bent top edges can be provided for a larger support surface and use of thinner walls for the supports;
the height of the hollow interior varies, with a 2 cm height being provided in one embodiment so that the outer sidewalls and base wall all have a same length for a square cross-sectional shape. However, a higher height of the side walls may be preferable to ensure proper assembly in a ground support and avoid any confusion or improper placement into slots in the ground support;
the first and second membranes are glued or adhered, for example with a silicone-based adhesive, to the top edges of the walls of the support structures, with the membrane preferably being stretched taut widthwise and/or lengthwise, although the membrane can simple be laid on the adhesive as well without widthwise or lengthwise stretching. The gluing or adhering provides a simple manufacturing method;
the first and second supports have closed first inlet ends. This advantageously allows the inlet of the channels to be sealed by an inlet manifold extending over the supports;
the first membrane extends over the first end of the first support, which allows longitudinal stretching of the membrane and a tauter longitudinal fit of the first membrane. Previous designs had permitted widthwise tautness that sometimes resulted in ridges extending widthwise during attachment of the membrane to the support structure. The first membrane can alternately or additionally extend over the outlet end of the first support; and alternately or additionally the second membrane can be similarly attached to the second support;
an inlet manifold surrounds and seals both the first and second membrane support structures, the inlet ends of the support structures being water-tight so water to be filtered presses against the inlet ends but does not enter the support structures and only enters the inlet. This structures advantageously greatly simplifies sealing of the inlet, and the fact that unfiltered water rests against the support structures surprisingly has no effect on the operation of the device and actually the inlet manifold can aid in sealing the first and second membrane supports toward each other to, for example, increase sealing by the channel structure between the first and second membranes;
the inlet manifold can be heat shrunk, for example by polythene tube, or can include an elastic tube that is stretched over the first and second ends of the first and second support structures. The other end of the manifold can be easily attached to a height regulator, for example a plastic tube that can be used to set the inlet pressure;
the inlet manifold can supply a plurality of modular water filters defined by a first and second support with the first and second membranes, supported widthwise for example in a ground support;
the first and second supports can support both the first and second membranes and a channel structure, either integral with the membranes as described above, for example side tapes or structuring on the membranes, and thus define first and second mating components of the filter. Preferably the structures can be identical on both the first and second mating components, and an outlet splitter then placed between the first and second components at the outlet to create a simply created and efficient outlet structure. For example copper foil of 30 micrometer thickness can be used to create a waste water outlet, and simply wrapped around the second outlet structure to create an outlet channel;
the outlet splitter can be a separate tube for example with a hollow U-shaped PVC or other plastic support having a hollow U-shaped interior matching the exterior dimensions of one or both of the first and second supports and a side wall of the membrane. The dimensions of the splitter support tube hollow interior thus could be 2.5 cm wide and 2.5 cm, and the splitter support walls can be 0.5 cm thick. A steel blade, with a 5 to 15 micrometer thick edge and becoming thicker, for example 100 micrometers thick, can be adhered over the longitudinally extending opening of the splitter support tube, for example with two sided adhesive tape having a thickness similar to the side walls of the membrane, for example 125 micrometers thick. The splitter support also could be made of elastic materials such as rubber, with the steel blade supported therein, as the steel blade positioning is aided by the side walls and sandwiched at the proper position between the two membrane side walls and any ridges;
the walls of the U-shaped splitter support can be closed by a cross wall downstream of the steel blade to reduce metal cost, and to allow a support for the steel blade and a base for waste water to flow over;
the outlet splitter can be manufactured entirely from plastic, for example having a PVC 30 micrometer thick edge at the splitter side, the outlet splitter preferable then having a hollow interior with a thickness equal to an outer thickness of the support added to a side wall thickness, for example 2.5125 cm. The splitter can have 0.5 cm walls that narrow or taper, preferably on a side facing the clean filtered water down to 30 micrometers or less between the membranes;
the splitter supports at a downstream end can connect to a perpendicular waste water collector, for example via a closed flexible tube with openings attaching to the ends of the splitter supports. This structure is advantageous if harmful particles such as PFOAS or PFOS are being filtered, and allows for sealed capture of the waste water. However, gravity and a simple sloped perpendicular open gutter could be used to capture the waste water;
the first and second mating components advantageously can be designed to be identical and modular. Each can support the respective membrane on one side and be either gas tight to permit for example carbon dioxide pressures of 1.3 atm and up to for example 2 atm or more, or openable to permit air to enter. More than one set of first and second components can sit side by side and be connected together by a larger inlet manifold, and share a single outlet splitter (or having individual ones), so that for example a diffusiophoretic water filtration device a whole field a meter or more wide can be created, and large scale municipal water filtration devices operated;
each modular pair of mating components can be monitored for proper flow and easily and inexpensively replaced. For example a flow or water presence sensor can be placed at each outlet splitter support, preferably monitoring the waste water stream. If a defect is ascertained, the device stopped and the components can be easily replaced, simply by sliding in a new modular pair or one of the defective supports;
a ground support can be used to permit multiple sets of mating components to slide into the ground support, and allow easy construction of large scale filter. The support can be shorter than the membrane supports to allow the outlet splitter space to fit between module pairs. The support could also be shorter at the inlet side, and allow for a rubber seal or extra sealing at the inlet;
the first and second membrane supports each have at least one hole or longitudinally extending slot to permit air to enter the support. The slot can be sealed by a mating rubber or other seal, for example at the bottom support surface of the ground support, so that the bottom support is sealed to define a gas delivery component of the mating components. The top support can remain open to atmosphere due to the hole or slot. The slot of the gas delivery membrane support also can simply be closed with duct tape, preferably inside the membrane support, or closed simply using the bottom of the ground support, even if the seal is not perfect;
the outlet end of the first and second supports opposite the sealed inlet first end can be open, or preferably be a closed end with a hole for a gas attachment;
a gas delivery tube can attach to the hole of the gas delivery component of the mating components to define a gas inlet while the hole of the other mating component can remain open to atmosphere. If open, the entire end can for example be sealed with a rubber stopper having a hole connecting to a gas delivery tube.
a perpendicular running gas delivery tube can deliver a gas such as CO2 to a plurality, even hundreds or more, of side-by-side gas delivery components, with the tube having side tubes connecting to the gas inlets;
the ground support has a plurality of side-by-side longitudinally extending slots into which a pair of the first and second mating components fit, preferably tightly. An interior width of the slot preferably thus is matched to an exterior width of the first and second mating components and most preferably to a width of the first and second supports. Any membrane width, if present, extending over the outside of the support can discounted and the support walls can aid in sealing the membrane. The ground support thus may for example be made of PVC and have a wall width of 1 cm throughout, with legs supporting the structure off the ground. If the supports are 80 cm long, in one embodiment, the ground support is 60 cm long, sits on 4 10 cm square legs and has widthwise 20 slots each 2.5 cm wide with 19 1 cm wide walls in between and 1 cm wide end sides for a total width of 61 cm. The slots in this embodiment are 5 cm high to support the first and second supports, which are 2.5 cm high and spaced by the side walls. Any small extension of the mating component pair out of the slot is advantageous, as it pressing on the extension, for example by a weight, can aid in sealing the side walls together and thus sealing the diffusiophoretic flow channels;
if only one mating pair is used, the ground support can have a single slot;
the outside walls of the components pairs and the ground support side walls preferably are flush, so that the only opening on the front end of the structure are the diffusiophoretic flow channels. Additional seals or sealants can be used to prevent leakage, although minor leakage, for example at the sides of end walls, advantageously can be tolerated, and perfect sealing is advantageously not required. The entire filtration device can sit on a collection surface so that any dripping water can be collected and if desired returned to the water source to be filtered;
the water pressures used, typically on the order of 30 to 70 mbar, advantageously are not so high as to create large pressures as slow flows are desired to permit laminar flow and aid diffusiophoretic action by increasing dwell time in the channels, and can be set for example by having the water to be filtered remain around a setpoint height of chosen from a height of about 30 to 70 cm above the outlet(s);
the inlet manifold advantageously can then surround the entire inlet face of the support structure, which at the front end sites off the ground, as the legs can be recessed downstream;
a top plate can be set over the top of the ground support and press down on the top mating component to aid in sealing the side walls and the inlet face, and the inlet manifold can fit around the outside walls of the support structure and the top plate at the inlet face;
a downstream end of the first and second mating components extends freely in a cantilevered fashion out of the ground support, for example 10 or 20 cm of an 80 cm long component, so that the outlet splitters have space in the widthwise direction. The outlet splitter walls thus can have half a thickness of the ground support slot walls, which space the pairs of mating components apart, for example, 1 cm, in the widthwise direction;
filtered water can be collected simply via gravity by a perpendicularly running collection gutter that can be sloped. However the outlet splitter could have closed pipes for both the waste and filtered water;
the diffusiophoretic action can be easily reversed, for example by having the CO2 delivered to the top of the mating components and the top components sealed for example via a top plate, and the bottom components spaced from the bottom of the ground support for example by spacers so they are open to atmosphere. The filtered water of filtered for negatively charged colloidal particles for example can be run through a companion or the same device to filter positively charged particles if desired, and visa-versa;
vertical scalability can be provided with easily in a single ground support with spacers in higher slots, or with stacked ground supports, and either pump driven pressure for the inlet or an inlet manifold with stepped reservoirs, so that pressure for each row is the same;
slots and pins in the ground support and membrane supports can aid positioning, especially in the longitudinal direction, and still provide some vertical play.
The present invention also provides a diffusiophoretic membrane support having a longitudinally-extending first hollow interior. The present invention also provides a plastic supported diffusiophoretic water filter. The present invention also provides a modular diffusiophoretic water filter having first and second mating components defining a water channel. The present invention also provides a slotted ground support for a diffusiophoretic water filter. The present invention also provides a removable mating outlet splitter. The present invention also provides a perpendicular running collection gutter running perpendicular to a plurality of diffusiophoretic water channels. The present invention provides a diffusiophoretic water filter with a sealed front face, sealed except for the diffusiophoretic water channels. The present invention provides an inlet manifold covering a front face of a diffusiophoretic water filer having a plurality of channels extending downstream from the face. The present invention also provides a method for modularly assembly of a diffusiophoretic water filter. The present invention proved a method for repairing a diffusiophoretic water filter by replacing a modular component of the water filter. Other inventions are contained herein and may be broader than the concepts listed above.
A PDMS block can for example be made of silicone rubber blocks or sheets available from for example Rubber-Cal Inc. in St. Ana, Calif.
Some preferred embodiments are disclosed below:
Additional
Membrane supports 1014, 1016 can be similar to supports 514, 516 in
A top 1402 (
A ground support 1400 can hold for example 50 modules vertically for a height around 1.5 meters, and have 2 cm thick walls so that 40 slots and modules horizontally is about 1.8 meters in width. With three channels per channel set C1 of 250 micrometers (125 micrometer half channels) and a width of 0.3 cm, at a pressure of 30 mbar flow is estimated as laminar with a Reynolds number of 11.8 and a velocity of 0.0256 m/s and a flow rate of 1.15 ml/min. A dwell time in the 80 cm long channel is 39 seconds giving time for many particles to move 200 micrometers via diffusiophoretic motion. A 50/50 split at 125 micrometers thus given a good filtering effect on the 250 micrometer wide stream, and clean water flow of 0.575 ml/min. With 200 channels sets and 600 channels, the device can produce 345 ml/min of clean water or 20.7 liters per hour. Higher throughputs with higher pressures are also possible and larger channel sizes are also possible.
Length L, width W and all the other dimensions can be application and material specific. It may be for example that widths of 15 or 30 cm for the membrane supports 24, 26 and membranes 14, 16 are preferred, and many more channels provided widthwise. This can reduce the number of CO2 and colloid input connections and base support slot material, as well as providing more channels per unit width.
An oversized length of the membranes 24, 26 and precision of placement in the lengthwise direction advantageously has little impact on the functioning of the filter, and in fact extra length L2 can be used to stretch and place precut membranes 24, 26 on their respective supports as shown in
The thicknesses and channel sizes of the membranes 14, 16 also may be varied, particularly it may be desirable to have a thicker PDMS base with CO2 channels 805 cut into the side opposite the colloid channels C between PDMS material support on longitudinal supports 112, as shown in
As shown in
The sheet 4010 can be unwound another meter and processed again so that a continuous sheet of perpendicularly extending channels, for example 100 meters long can be produced. A cutter C can cut the sheet to any desired location in direction U, which can then define the width of water filter, with SW generally defining the length.
As shown in
As similar manufacturing and construction can be used for sheets where the channels are simply cut all the way through to the second end by lasers LA (
An easily manufactured and high output device thus can be provided, and can extend for example 100 meters or more in length easily.
This claims the benefit of U.S. Provisional Application Nos. 62/778,847, filed Dec. 12, 2018, 62/780,910, filed Dec. 17, 2018, 62/783,168, filed on Dec. 20, 2018, 62/784,728, filed on Dec. 25, 2018, 62/783,366, filed Dec. 21, 2018, 62/784,310, filed Dec. 21, 2018, 62/784,511, filed on Dec. 23, 2018 and 62/786,399, filed Dec. 29, 2018. All of the above listed patent applications are hereby incorporated by reference herein.
Filing Document | Filing Date | Country | Kind |
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PCT/US2019/065976 | 12/12/2019 | WO | 00 |
Number | Date | Country | |
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62778847 | Dec 2018 | US | |
62780910 | Dec 2018 | US | |
62783168 | Dec 2018 | US | |
62784310 | Dec 2018 | US | |
62783366 | Dec 2018 | US | |
62784511 | Dec 2018 | US | |
62784728 | Dec 2018 | US | |
62786399 | Dec 2018 | US |