System and method for sorbtion distillation
10464825 ยท 2019-11-05
Inventors
Cpc classification
Y02B10/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/28004
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28014
PERFORMING OPERATIONS; TRANSPORTING
H02S40/44
ELECTRICITY
H01L31/0547
ELECTRICITY
B01D15/08
PERFORMING OPERATIONS; TRANSPORTING
F24S23/77
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02W10/37
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E10/60
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/20
PERFORMING OPERATIONS; TRANSPORTING
Y02B10/70
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F24S23/79
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J20/046
PERFORMING OPERATIONS; TRANSPORTING
Y02E10/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E10/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F28D15/0275
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
B01J20/04
PERFORMING OPERATIONS; TRANSPORTING
B01J20/20
PERFORMING OPERATIONS; TRANSPORTING
F24S23/77
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F24S20/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F24S23/79
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H02S40/44
ELECTRICITY
H01L31/054
ELECTRICITY
B01D15/08
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A system for distilling water is disclosed. The system comprises a heat source, and a plurality of open-cycle adsorption stages, each stage comprising a plurality of beds and an evaporator and a condenser between a first bed and a second bed, wherein each bed comprises at least two vapor valves, a plurality of hollow tubes, a plurality of channels adapted for transferring water vapor to and from at least one of the condenser or the evaporator, a thermally conductive water vapor adsorbent, and wherein each vapor valve connects a bed to either the condenser or the evaporator.
Claims
1. A distillation system, comprising: a plurality of operatively connected open-cycle adsorption stages, including a first stage and a second stage, each stage comprising: a plurality of operatively connected beds, including a first bed and a second bed; and an evaporator and a condenser operatively connected to the first bed and the second bed; a switchable heat source configured to provide heat to one of the plurality of operatively connected beds in one of the plurality of operatively connected open-cycle adsorption stages only during a first operating phase to desorb water vapor; and a switchable heat exhaust configured to remove heat from another of the plurality of operatively connected beds in one of the plurality of operatively connected open-cycle adsorption stages only during the first operating phase to remove the heat of adsorption; wherein each bed comprises at least a first, second, and third vapor valve, at least one hollow tube, at least one channel adapted for transferring water vapor to and from at least one of the condenser or the evaporator, and a thermally conductive water vapor adsorbent, wherein the first vapor valve connects the bed to the condenser, the second vapor valve connects the bed to the evaporator, and the third vapor valve connects a volume inside the hollow tubes of the first bed with a volume inside the hollow tubes of the second bed, wherein the distillation system is configured to transfer both a sensible heat and a heat of adsorption from the second bed of each stage to the first bed of the subsequent stage, excepting the last stage, wherein a temperature of the first bed of a respective subsequent stage is lower than a temperature of the second bed of a respective previous stage, during the first operating phase, wherein the distillation system is configured to desorb water vapor from the first bed of each stage into the condenser of each stage and adsorb water vapor from the evaporator of each stage into the second bed of each stage during the first operating phase, wherein the distillation system is configured to transfer both a sensible heat and a heat of adsorption from the first bed of each stage to the second bed of the same stage, wherein a temperature of the second bed of each stage is lower than a temperature of the first bed of the same stage, during a second operating phase, and wherein the distillation system is configured to desorb water vapor from the second bed of each stage into the condenser of each stage and adsorb water vapor from the evaporator of each stage into the first bed of each stage during a second operating phase.
2. The distillation system of claim 1, wherein each evaporator and condenser is shared between the first bed and second bed of each of the respective stages, wherein the evaporator is capable of receiving both a sensible heat and a heat of vaporization from the condenser to generate water vapor from solution comprising water and at least one dissolved impurity, and wherein each evaporator is configured to receive a solution comprising water and at least one dissolved impurity, the solution having a temperature predetermined to suit the equilibrium uptake of an adsorbent, where a suitable temperature is determined by first selecting both a desired operational temperature range and uptake range for the adsorbent, then selecting the solution temperature such that the saturated water vapor partial pressure corresponds to the desired adsorbent temperature and uptake range.
3. The distillation system of claim 1, wherein the hollow tubes are comprised of at least one material selected from a group consisting of copper, aluminum, and steel, and wherein the thermally conductive water vapor adsorbent is comprised of a porous media, at least one material selected from a group consisting of calcium chloride, lithium bromide, and lithium chloride, and a plurality of graphite nanosheets, each graphite nanosheet having between about 1 and about 100 carbon atom planes in thickness, and having a characteristic diameter of less than 300 microns.
4. The distillation system of claim 1, wherein a volume in the first bed is a volume defined as the sum of the volume inside the hollow tubes of the first bed plus the volume of a vapor plenum; wherein the third vapor valve is adapted for allowing controlled vapor flow and heat transfer between beds; wherein the volume in the first bed can be evacuated of non-condensable gases and selectively filled or drained of a volatile fluid to allow the volume to generate or condense vapor, respectively; wherein heat from the thermally conductive water vapor adsorbent conducted through the hollow tube wall into the volume of the first bed vaporizes at least some of the volatile fluid at a first temperature, after which the vaporized fluid is transmitted and condensed in the volume within the second bed which is at a second temperature lower than the first temperature; and wherein, when heat from the thermally conductive water vapor adsorbent is not vaporizing at least some of the volatile fluid, the system is capable of having vapor generated from a second bed or the heat source at a third temperature higher than the second temperature flow into the volume of the first bed and condense, conducting heat out of the volume through the hollow tube wall and into the thermally conductive water vapor adsorbent.
5. The distillation system of claim 1, wherein the operational range in temperature and adsorbed water uptake for each bed is selected, based on the physical equilibrium properties of the adsorbent, to correspond with the saturated vapor partial pressure of the input solution at a particular temperature; the resultant operational temperature ranges of all beds of all stages forming a continual sequence between the temperatures of the heat source and the heat exhaust.
6. The distillation system of claim 1, further comprising a pre-deaeration unit that receives an input liquid, and outputs a deaerated liquid to the first open-cycle adsorption stage.
7. The distillation system of claim 1, further comprising at least one heat exchanger for transferring heat between fluid entering at least one of the evaporators from the plurality of operatively connected open-cycle adsorption stages and at least one fluid exiting from at least one component selected from the group consisting of the condenser from at least one of the plurality of operatively connected open-cycle adsorption stages and the evaporator from at least one of the plurality of operatively connected open-cycle adsorption stages.
8. The distillation system of claim 1, further comprising an electrical power source.
9. The distillation system of claim 8, wherein the power source comprises a plurality of solar cells.
10. The distillation system of claim 4, wherein the system is configured such that the heat of adsorption generated by the second bed of a final stage of the plurality of operatively connected open-cycle adsorption stages is capable of being exhausted externally.
11. The distillation system of claim 1, wherein the first stage operates at temperatures between 105 C. and 210 C., and the plurality of stages comprises at least three stages.
12. The distillation system of claim 1, further comprising a plurality of solar cells configured to provide electrical power for the distillation system, and a plurality of solar thermal collectors adapted to provide thermal power for the distillation system.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
(8) The disclosed adsorption distiller uses an adsorption bed to reduce the water vapor partial pressure above the evaporator, making the vaporization of water more efficient by reducing the required thermal drive. By recycling both the latent energy of vaporization and the heat of adsorption 32 times from the heat source to the heat exhaust, this cycle can achieve a Performance Ratio of 28, or 23 kWh thermal energy +0.1 kWh electrical energy per cubic meter of distilled water, when losses are included. This is about 3 times more efficient than existing thermal distillation techniques such as Multi-Stage Flash (MSF), Multiple Effect Distillation (MED), and at least 30 times more efficient than single-effect solar stills. Due to its simple design and the use of commodity adsorbent materials, a bill of a materials analysis estimates a reasonable cost for a 60 m.sup.3/day solar-powered distiller which includes solar collectors and gravity-driven sand pretreatment. Because the distiller does not consume electricity or membranes, is highly automated, and requires modest pretreatment, the breakeven cost of water is relatively low without financing costs, even with moderate interest rates, assuming a 25 year distiller life.
(9) The adsorption distiller uses an inexpensive industrial nanomaterial, silica gel, as a highly porous matrix for a hygroscopic salt, calcium chloride. This composite of hygroscopic calcium chloride impregnated in the internal pore surfaces of mesoporous silica gel has been studied since its discovery in 1996 by Aristov who called it a Selective Water Adsorbent (SWS). Note that there can be some ambiguity in the terminology used to describe the reaction, because while chemical absorption is occurring, reaction kinetics is enhanced by using an adsorbent to increase surface area and vapor transport. As described herein, the words adsorption and adsorbed are used to describe the reaction. Mesoporous silica gel has an average pore diameter of 15 nm with surface areas of, in many cases, about 400 m.sup.2/gram but is relatively inexpensive. By confining a salt within the silica gel pores, SWS boosts uptake (adsorbed water mass per mass of adsorbent) above the physical adsorption capacity of silica gel. SWS also maintains a solid state with a very large reaction surface area. In the envisioned design, a single 16 stage distiller packaged in a shipping container would have a vapor adsorption area of 4160 square kilometers, more than the area of Rhode Island.
(10) The adsorption distiller consists of a number of open-cycle adsorption stages connected in series, where the exhaust heat from an upper stage is used to drive the next stage. In a thermally driven heat pump, heat from a hot source is used to move heat from a cold evaporator to a warmer condenser. In the adsorption distiller, the evaporator and condenser are kept nearly isothermal using a high heat transfer coefficient flat plate condenser/evaporator. Since the source of water vapor is from the input liquid being distilled, this configuration maximizes the number of adsorption/desorption steps for any given temperature gradient. In the adsorption distiller, two features lead to the improvement in performance ratio. First, a large number of stages are chained serially. Second, the adsorption beds are arranged in such a way that one half of the cycle thermally drives a pair of adsorption beds out of equilibrium, while the other half is a relaxation towards equilibrium that requires no energy input. Since both halves of the cycle generate distillate, the theoretically efficiency is equal to the number of beds, or double the number of stages since each stage has a pair of adsorption beds.
(11) Adsorption heat pumps based on silica gel have been studied for many years. However, one of the major difficulties with any silica gel based system has been inefficient heat transfer due to the low thermal conductivity of silica gel. The heat of adsorption has a value within 5-10% of the heat of vaporization, and can quickly raise the temperature of the adsorbent and slow or stop the adsorption process if not effectively removed. Previous attempts have used clay binders, waterglass, and conductive epoxies to thermally couple the silica gel with expensive extended metal heat sink structures. This issue is particularly important for the adsorption distiller as it relies on small temperature differentials, so the adsorbent temperature cannot elevate significantly during adsorption. We have based our design on a promising solution.
(12) One approach uses expanded graphite, which can be thought of as a graphene precursor, where graphite particles have been sheared apart to a low number of carbon planes. When mixed with silica gel and mechanically compressed, the planar graphite particles align into sheets and dramatically improve inter-particle thermal transport in the plane perpendicular to the compression direction, increasing the in-plane thermal conductivity to 19 W/(m.Math.K), a several hundred-fold improvement. The improvement in thermal conductivity and the recent availability of industrial quantities of expanded graphite and graphene precursors, allow us to design a greatly simplified adsorption bed using an array of vertical tubes to form a closed-loop boiler that conveys the heat of adsorption between stages using water vapor.
(13) While flakes having a many layers are envisioned, the graphite flakes preferably have 100 layers of carbon planes or less. One embodiment comprises flakes having 100 layers of carbon planes in each flake, or a flake thickness of about 0.034 micron. Another embodiment comprises flakes having 50 layers of carbon planes in each flake. Another embodiment comprises flakes having 25 layers of carbon planes in each flake. Another embodiment comprises flakes having 10 layers of carbon planes in each flake. And yet another embodiment comprises flakes having 1 layer of carbon in each flake.
(14) Additionally, while flakes may be of any dimensions, the graphite flakes are preferably below 300 microns in size (roughly 48 mesh or larger). One embodiment comprises flakes between 180 and 300 microns in size (approximately 48 to 80 mesh). Another embodiment comprises flakes between 150 and 180 microns in size. Another embodiment comprises flakes between 75 and 150 microns. And another embodiment comprises flakes less than 75 microns in size.
(15) Additionally, while any concentration of graphite is envisioned for the graphite-salt composition, compositions comprising 50% or less graphite by weight are preferred. One preferred embodiment comprises between 15-30% graphite by weight. In one embodiment, the composition is binary, with the salt in silica gel making up the remainder of the weight. However, in other embodiments, the composition also includes additional materials, including but not limited to biologics, polymers or catalysts.
(16) Cycle Operation
(17) The disclosed system's cyclical operation is shown schematically in
(18) Each bed has an upper and lower temperature limit, where there is preferably less than about 20 C. difference between the upper and lower limit, and more preferably less than about 10 C. difference. The highest upper temperature being in the first hot chamber (21), which preferably has a temperature range of about 105 to 210 C., and more preferably from 143.5 to 150.0 C. As will be seen, the lower temperature limit of one chamber is the upper temperature limit of the next chamber. In this figure, the first hot chamber (21) is connected with the first cool chamber (22), and the first cool chamber (22) preferably has a temperature range of about 138.1 to 143.5 C., or a narrow range (typically less than about 6 C.) below that of the first chamber. The next chamber is the second hot chamber (23) which preferably has a temperature range of about 133.5 to 138.1 C., or a narrow range (typically less than about 6 C.) below that of the first cold chamber. The second cool chamber (24) preferably has a temperature range of about 129.5 to 133.5 C., or a narrow range (typically less than about 5 C.) below that of the second hot chamber. The third chambers (28) and (29) have preferred temperature ranges of about 125.6 to 129.5 C. and about 122.2 to 125.6 C., respectively. Fourth chambers, if they had been depicted, would have preferred temperature ranges of about 119.2 to 122.2 C., and about 116.4 to 119.2 C., respectively.
(19) Like adsorption chiller cycles, half of each stage is adsorbing for half of the cycle and desorbing for the other half. However, unlike chiller cycles, this cycle produces no heat pumping effect. To distinguish the two phases of operation, the term forcing is used when heat is input to drive the two adsorbent beds in each stage out of equilibrium, and relaxing when the beds are allowed to return to equilibrium.
(20) As shown in
(21) As shown in
(22) The schematics shown in
(23) The heat transfer tubes and vapor plenum (
(24) One embodiment of a single adsorption bed (200) is shown in
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(26) In one embodiment shown in
(27) By connecting adsorbent coils in parallel with a manifold, minimizing flow lengths, and using efficient pumps, the total electrical energy intensity for the cycle may be reduced to 0.5 kWh/m.sup.3 or less. This can be generated with a bank of photovoltaic (PV) panels.
(28) In one embodiment, the only surface to contact brine will be one side of the evaporator/condenser, which will not only be designed for automated acid or chemical cleaning of scale build-up, but is also a maintainable component than can be disassembled and pressure washed. This is in contrast to typical MED plants with extended heat transfer surfaces which can be difficult to maintain.
(29) In one embodiment, manufacturing is relatively simple due to the low component count. Each distiller is assembled from a large number of identical adsorption stages. As shown in
(30) For the purpose of illustrating how the cycle works, this disclosure refers to a two stage system as shown in
(31) In the Forced (i.e., heat-driven) phase, first bed (21) is heated by condensing vapor in the boiler tubes generated by the heat source (20). Condensed water in the boiler tubes is pumped back to fill the boiler tubes in the heat source, as indicated by the line (50) just below the bed and the heat source.
(32) The first bed (21) is open to the condenser, and the increase in temperature causes the adsorbent to desorb vapor increasing the water vapor pressure and temperature in the condenser. This causes condensation and a transfer of the heat of vaporization to the input water in the evaporator. The second bed (22) is open to the evaporator and its boiler tubes are full and transferring heat to the third bed via vapor (23). The cooling of the second bed (22) causes it to adsorb the vapor from the evaporator. The heat of adsorption from second bed (22) will continue to transfer to third bed (23) until it reaches the equilibrium uptake at the lower temperature.
(33) Second stage beds (23 and 24) started at the same temperature, but with third bed (23) receiving heat from second bed (22), it will also desorb vapor which will condense and evaporate more input water which will be adsorbed by fourth bed (24). The final bed exhausts adsorption heat to a condenser (25) cooled by the final residue water, distillate, and cooling water.
(34) At the end of the forcing phase, the adsorption beds have become separated in temperature and uptake, with each of the hot beds hotter and drier than the cold beds in each stage. The relaxation phase connects the hot and cold beds of each stage (i.e., 21/22, 23/24) to allow them to come back to equilibrium. As heat transfers from the hot to cold bed, the cold bed desorbs vapor into the condenser, which in turn evaporates input water adsorbed by the hot stage.
(35) Adsorption Uptake Equilibrium and Kinetics
(36) The adsorption distillation cycle depends on the pull-push action of the adsorbent to pull vapor when adsorbing and push when desorbing, so a discussion of adsorbent equilibrium and kinetics is necessary.
(37) The equilibrium uptake (kg/kg, adsorbed water mass per mass of adsorbent) of the adsorbent has been measured and published by others and can be fitted as a function of a single variable, the free energy of adsorption, F=RT.Math.ln(P.sub.water/P.sub.saturated), where P.sub.saturated is the saturated water vapor pressure at the temperature of the adsorbent. There were no significant differences between fits using Aristov's formulas based on the Dubinin-Polanyi potential or fits using Tth's equation used by Chua. A computer program based on these equations was written to calculate cycle parameters. A plot of the equilibrium uptake of the adsorbent is shown in
(38) In
(39) To make the plot easier to read, the y-axis is plotted as the temperature of the water with the saturated vapor pressure rather than the typical logarithmic vapor pressure scale. This is done because we are interested in the temperature of the water in the evaporator, which determines the vapor pressure over the adsorbent.
(40) The operating range of each adsorption bed (320) is shown overlaid on the uptake contours (310) in
(41) In one embodiment, the uptake change for each bed is designed for 3.2%. With 325 kg in each bed, 32 total beds, and a cycle time of 480 s, the daily output from one distiller is 60 m.sup.3. The design includes sufficient solar collection and hot water storage with a swing from 150-180 C. to power the distiller during nighttime.
(42) Adsorption kinetics determines the water production rate. One embodiment of a cycle has been designed using the linear driving force kinetic equation found in a number of published journal articles from independent research groups. In this embodiment, each stage is designed for an uptake swing of 0.034 kg/kg within 6 minutes. Adsorption beds at lower temperatures in
(43) One embodiment of this system uses a serial flow pattern to achieve high recovery ratios (80%), where most of the water is extracted from the brine, rather than discharged. This can be increased further for wastewater remediation applications where minimal residual discharge is desirable.
(44) Top Brine Temperature for Seawater Desalination
(45) One example design, similar to that illustrated in
(46) The top brine temperature in one embodiment was selected to remain below 120 C. to stay below the solubility limit of hard CaSO.sub.4 scaling. The brine flow is serial from one evaporator to the next in decreasing temperature order and increasing salinity, as seen in
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(49) System Integration and Packaging
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(51) The thermal collector arrays and PV arrays may be deployed outside the housing units, while the adsorption modules operate inside the housing units. In some embodiments, the housing units may be behind PV arrays, and may act as support structures for the PV arrays. These housing units may be located in practically any location, including near water sources such as oceans or seas.
(52) Table 1 summarizes specifications for one embodiment of the desalination unit.
(53) TABLE-US-00001 TABLE 1 Water production (annual average) 60 m.sup.3/day or 16000 gpd Thermal GOR/PR ~28 Energy intensity 23 kWh.sub.th + 0.1 kWh.sub.e/m.sup.3 Adsorption cycle time 480 s Adsorbent mass per bed 325 kg Recovery Ratio 72% Land footprint 400 m.sup.2 or 4306 ft.sup.2 Solar thermal collection area 450 m.sup.2 (incl. night storage) PV panel installed watts 2250 W (incl. night storage) Assumed insolation 5 kWh/m.sup.2/day
(54) Other Features
(55) Exergy efficiency on the adsorption distiller can be optimized in real time to maximize water production based on changing conditions. Optimization may be based on only three (3) input parameters: input heat temperature, exhaust temperature, and the amount of heat available. The only actuators for control may be the switching times and durations of the relaxation and heat driven modes. Automation of the process can occur using a real-time optimized controller using a low-power embedded computer with cellular connectivity, such as the Raspberry Pi and/or Particle Electron, to allow remote control and data logging of operational units worldwide.