阅读说明：本技术 基于金属有机骨架的水捕获设备 (Water capture device based on metal organic framework ) 是由 泽维尔·穆莱特 克里斯蒂娜·康斯塔斯 A·桑顿 马蒂亚斯·赫塞尔曼 斯蒂芬·赫尔曼 于 2019-08-16 设计创作，主要内容包括：一种用于从含水气体中捕获水分的设备,该设备包括：壳体,所述壳体具有含水气体可以流入其中的入口；水吸附剂,所述水吸附剂位于壳体中,所述水吸附剂包括至少一种能够从含水气体中吸附水分的水吸附金属有机骨架复合材料；以及水解吸装置,所述水解吸装置与水吸附剂接触和/或围绕水吸附剂,所述水解吸装置在(i)停用状态和(ii)激活状态之间是选择性地可操作的,在激活状态中,所述装置被配置成向水吸附剂施加热量、减压或其组合,以从水吸附剂中解吸水分。(An apparatus for capturing moisture from an aqueous gas, the apparatus comprising: a housing having an inlet into which aqueous gas may flow; a water adsorbent located in the shell, the water adsorbent comprising at least one water-adsorbing metal-organic framework composite capable of adsorbing moisture from an aqueous gas; and a water desorption device in contact with and/or surrounding the water adsorbent, the water desorption device being selectively operable between (i) a deactivated state and (ii) an activated state in which the device is configured to apply heat, reduced pressure, or a combination thereof to the water adsorbent to desorb moisture from the water adsorbent.)

1. An apparatus for capturing moisture from an aqueous gas, the apparatus comprising:

a housing having an inlet into which the aqueous gas can flow;

a water adsorbent enclosed within the housing, the water adsorbent comprising at least one water-adsorbing metal-organic framework composite capable of adsorbing moisture from the aqueous gas; and

a water desorption device in contact with and/or surrounding the water adsorbent, the water desorption device being selectively operable between (i) a deactivated state and (ii) an activated state in which the device is configured to apply heat, reduced pressure, or a combination thereof to the water adsorbent to desorb moisture from the water adsorbent.

2. The apparatus of claim 1 wherein said hydrolysis suction means comprises at least one heat transfer means in direct thermally conductive contact with said water adsorbent.

3. The apparatus of claim 2, wherein the heat transfer device is in thermally conductive contact with a heating device.

4. The apparatus of claim 2 or 3, wherein the heat transfer means comprises at least one heat transfer element extending from the heating means to the water adsorbent.

5. Apparatus according to claim 3 or 4, wherein the heating means comprises at least one Peltier device (thermoelectric heat pump).

6. Apparatus according to claim 5, wherein the Peltier device is capable of heating the packed bed to at least 50 ℃, preferably to at least 60 ℃, and more preferably to between 50 ℃ and 80 ℃.

7. The apparatus of any of claims 2 to 6, wherein the water adsorbent is contained within or coated on at least a portion of the heat transfer device.

8. An apparatus according to any one of claims 2 to 7, wherein the heat transfer means comprises a heat sink, preferably a heat sink having a plate or fin arrangement.

9. The apparatus of any of claims 2 to 8, wherein the heat transfer device comprises a plurality of spaced apart heat transfer elements, and wherein the water adsorbent is contained as a packed bed between at least two heat transfer elements.

10. The apparatus of claim 9, wherein the heat transfer element comprises a planar support element, preferably selected from at least one of a plate or a fin.

11. The apparatus according to claim 9 or 10, further comprising at least one fluid displacing device to drive a fluid flow through the packed bed, the fluid displacing device preferably comprising at least one fan.

12. The apparatus of claim 11, wherein the fluid displacing device produces at least 3m³H, preferably 3m³H to 300m³H fluid flow through the packed bed.

13. The apparatus of any one of claims 1 to 12, further comprising a condenser system for cooling the product gas stream from the water adsorbent.

14. Apparatus according to claim 5 or 6 or any one of claims 7 to 13 when dependent on claim 5 or 6, wherein each peltier device has a hot side and a cold side, wherein the hot side of each peltier device is in thermal communication with at least one heat sink and the cold side of each peltier device forms part of the condenser system.

15. The apparatus of claim 14, wherein the cold side of each peltier device is in thermal communication with at least one heat transfer device, preferably at least a heat sink.

16. The apparatus of any preceding claim, wherein the inlet comprises at least one fluid seal movable from an open position allowing gas to flow through the inlet to a closed position in which the inlet is substantially sealed closed to gas flow.

17. The apparatus of claim 16, wherein the fluid seal comprises at least one movable door, preferably at least one pivotable plate or wing, more preferably at least one louver.

18. The apparatus of any preceding claim, wherein the water adsorbent is a metal organic framework composite comprising:

at least 50 wt% of a water-adsorbing metal organic framework; and

at least 0.1 wt% of a hydrophilic binder.

19. The apparatus of claim 18, wherein the metal-organic framework composite comprises a coating applied to a surface of the water-desorbing device.

20. The apparatus of claim 18, wherein the metal organic framework composite comprises a shaped water-adsorbing composite having at least one average dimension greater than 0.5 mm.

21. The apparatus of claim 20, wherein the formed water-adsorbing composite has at least one average dimension greater than 0.8mm, preferably at least 1mm, preferably at least 1.2mm, and still more preferably at least 1.5 mm.

22. The apparatus of claim 20 or 21, wherein the formed water-adsorbing composite has an average width, an average depth and an average height each greater than 0.5mm, preferably greater than 1 mm.

23. The apparatus of claim 20, 21 or 22, wherein the shaped water-adsorbing composite comprises an elongated body having a circular or regular polygonal cross-sectional shape.

24. The apparatus of any one of claims 20 to 23, wherein the shaped water-adsorbing composite comprises an elongate body having a triangular cross-sectional shape, preferably an equilateral triangular cross-sectional shape.

25. The apparatus of any preceding claim, wherein the water-adsorbing metal-organic framework comprises at least one of: aluminum fumarate, MOF-801, MOF-841, including Co₂Cl₂M of BTDD₂Cl₂BTDD, Cr-soc-MOF-1, MIL-101(Cr), CAU-10, alkali metal (Li)⁺，Na⁺) Doped MIL-101(Cr), MOF-303, MOF-573, MOF-802, MOF-805, MOF-806, MOF-808, MOF-812, or a mixture thereof.

26. The apparatus of any preceding claim, wherein the water-adsorbing metal-organic framework comprises a plurality of multidentate ligands, wherein at least one ligand is selected from fumarate-or 3, 5-pyrazoledicarboxylic acid (H3PDC) -based ligands.

27. The apparatus of claim 26, wherein the metal ion is selected from Fe³⁺、Li⁺、Na⁺、Ca²⁺、Zn²⁺、Zr⁴⁺、Al³⁺、K⁺、Mg²⁺、Ti⁴⁺、Cu²⁺、Mn²⁺To Mn⁷⁺、Ag⁺Or a combination thereof, preferably Zr⁴⁺、Al³⁺Or a combination thereof.

28. The apparatus of any preceding claim, wherein the water-adsorbing metal-organic framework comprises aluminum fumarate.

29. The device of any preceding claim, wherein the water-adsorbing metal-organic framework has a pore size of at least 2nm, preferably greater than 5 nm.

30. An apparatus according to any preceding claim, wherein the water-adsorbing metal-organic framework has a particle size of less than 800 μm, preferably less than 600 μm, and more preferably less than 500 μm.

31. The apparatus of any preceding claim, wherein the shaped water-adsorbing metal-organic framework has at least 700m²G, preferably greater than 800m²Average surface area in g.

32. The apparatus of claims 18 to 24, wherein the hydrophilic binder comprises a hydrophilic cellulose derivative, preferably an alkyl cellulose derivative, a hydroxyalkyl cellulose derivative or a carboxyalkyl cellulose derivative.

33. The apparatus of any one of claims 18 to 24, wherein the hydrophilic adhesive is selected from at least one of: hydroxypropyl cellulose (HPC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose (CMC), or polyvinyl alcohol (PVA).

34. The apparatus of any one of claims 18 to 24, 32 or 22, comprising between 0.2 wt% and 5 wt% hydrophilic binder, preferably between 0.5 wt% and 3 wt% hydrophilic binder, more preferably between 0.8 wt% and 2 wt% hydrophilic binder, preferably about 1 wt% hydrophilic binder.

35. An apparatus according to any preceding claim, wherein the water-adsorbing metal-organic framework has a particle size of less than 500 μm, preferably less than 300 μm, more preferably less than 212 μm, and still more preferably less than 150 μm.

36. The apparatus of any preceding claim, wherein the water-adsorbing metal-organic framework has an average particle size of between 20 μ ι η and 100 μ ι η, preferably between 40 μ ι η and 80 μ ι η.

37. The apparatus of claims 18 to 24, further comprising less than 0.5 wt% lubricant, preferably less than 0.1 wt% lubricant.

38. The apparatus of claim 1, wherein:

the water adsorbent is formed from a shaped water-adsorbing composite comprising a mixture of at least 50 wt% of a water-adsorbing metal-organic framework and from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200nm, and

the hydrolysis sorption arrangement includes an Alternating Current (AC) magnetic field generator located within and/or about the water sorbent, the AC magnetic field generator configured to apply an AC magnetic field to the water sorbent.

39. The apparatus of claim 38, wherein the ac magnetic field generator comprises at least one induction coil positioned within and/or around the packed bed of the shaped water adsorption composite.

40. The apparatus of claim 38 or 39, wherein the water adsorbent comprises a shaped water adsorbent composite in a packed bed in the shell.

41. The apparatus of any one of claims 38 to 40, wherein the shaped water-adsorbing composite is filled at a density of from 0.10 to 1.0kg/L, preferably 0.25 to 0.5kg/L, and more preferably between 0.25 and 0.35 kg/L.

42. The apparatus according to any one of claims 38 to 41, wherein the magnetic particles comprise ferromagnetic particles, paramagnetic particles or superparamagnetic particles.

43. The apparatus of any one of claims 38 to 42, wherein the magnetic particles comprise a metal chalcogenide comprising a compound or ionic or elemental form of said compound comprising a metal M selected from Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi In combination with an element C selected from at least one of O, S, Se, Te.

44. The apparatus of any one of claims 38 to 43, wherein the magnetic particles comprise at least one of: MgFe₂O₄、Fe₃O₄C-coated Co, CoFe₂O₄、NiFe₂O₄Pyridine-2, 6-diamine functionalized SiO₂Or pyridine-2, 6-diamine functionalized Fe₃O₄。

45. The apparatus of any one of claims 38 to 44, wherein the magnetic particles comprise a plurality of magnetic nanospheres.

46. The device according to any one of claims 38 to 45, wherein the magnetic particles have an average particle diameter of less than 150nm, preferably between 1nm and 100 nm.

47. The apparatus of any one of claims 38 to 46, comprising between 0.5 wt% and 7 wt% magnetic particles, preferably between 1 wt% and 5 wt% magnetic particles.

48. The apparatus of any preceding claim, wherein the aqueous gas comprises ambient air.

49. The apparatus of claim 48, wherein the relative humidity of the ambient air is between 25% and 100% at 22 ℃, preferably between 40% and 100% at 22 ℃, more preferably between 40% and 80% at 22 ℃, preferably between 40% and 60% at 22 ℃, more preferably about 50% at 22 ℃.

50. A method of capturing moisture from an aqueous gas comprising at least one of the following cycles:

feeding an aqueous gas through an inlet of a housing and past a water adsorbent enclosed within the housing, the water adsorbent comprising at least one water-adsorbing metal-organic framework composite capable of adsorbing moisture from the aqueous gas, such that the water adsorbent adsorbs water from the aqueous gas,

operating at least one water desorption device to change from an inactive state to an active state, to apply heat, to depressurize, or a combination thereof, to the water adsorbent so as to release at least a portion of the adsorbed water therefrom into a product fluid stream, and

directing the product fluid stream to a condenser system to separate moisture from the product fluid stream,

wherein the water desorption device is in contact with and/or surrounds the water adsorbent.

51. A method of capturing moisture from an aqueous gas using the apparatus of any one of claims 1 to 49, using the apparatus of claim 50.

52. The method of claim 50 or 52, further comprising the steps of:

closing the inlet of the housing prior to operating the at least one water desorption device.

53. The method of claim 50, 51 or 52, wherein one cycle of the method has a duration of less than 10 hours, preferably less than 8 hours, more preferably less than 7 hours, and more preferably 6 hours or less.

54. The method of any one of claims 50 to 53, wherein said operating said at least one water desorption device comprises operating at least one Peltier device to heat water adsorbent so as to desorb at least a portion of the adsorbed water therefrom into said product fluid stream.

55. The method of claim 54, wherein the at least one Peltier device forms part of a condenser system configured to cool the product fluid stream.

56. The process of any one of claims 50 to 53, wherein said operating said at least one water sorption arrangement comprises applying an alternating magnetic field to a packed bed of a shaped water-adsorbing composite comprising at least 50 wt% of a water-adsorbing metal-organic framework, thereby generating heat within the shaped water-adsorbing composite for releasing at least a portion of the adsorbed water therefrom into a product fluid stream; and at least 0.1 wt% of a hydrophilic binder and from 0.2 to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm.

57. The method of claim 56, wherein the method has a cycle time of less than 2 hours, preferably less than 1 hour.

58. The method of claim 56 or 57, wherein the alternating magnetic field is applied when the packed bed has adsorbed moisture equal to at least 75% of the packed bed's saturation point, preferably at least 80% of the packed bed's saturation point, more preferably at least 90% of the packed bed's saturation point.

59. The method of claim 56, 57, or 58, wherein the alternating magnetic field is applied for at least 1 second.

60. The method according to any one of claims 56 to 59, wherein the alternating magnetic field has a frequency between 250kHz and 280kHz, preferably from 260kHz to 270 kHz.

61. The method of any one of claims 50 to 60, which produces greater than 2.8L of water per kg of MOF per day at 20% relative humidity and 35 ℃.

62. An apparatus for capturing moisture from an aqueous gas, the apparatus comprising:

at least one heat transfer device in contact with a packed bed of a shaped water-adsorbing composite having at least one average dimension greater than 0.5mm and comprising at least 50 wt% of a water-adsorbing metal-organic framework; and at least 0.1 wt% of a hydrophilic binder; and

at least one Peltier device in thermal communication with each heat transfer device, each Peltier device configured to heat the shaped water-adsorbing composite to desorb water therefrom for entrainment into a product fluid stream,

wherein the at least one peltier device also forms part of a condenser system for cooling the product fluid stream from the packed bed of the shaped water-adsorbing composite.

63. An apparatus for capturing moisture from an aqueous gas, the apparatus comprising:

a housing containing a packed bed of shaped water-adsorbing composite in the housing, the shaped water-adsorbing composite having at least one average dimension greater than 0.5mm and comprising at least 50 wt% of a water-adsorbing metal-organic framework; at least 0.1 wt% of a hydrophilic binder and from 0.2 to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm; and

an Alternating Current (AC) magnetic field generator positioned within and/or about the packed bed of the shaped water-adsorbing composite, the AC magnetic field generator configured to apply an AC magnetic field to the packed bed of the shaped water-adsorbing composite.

64. The apparatus of claim 62 or 63, wherein the water-adsorbing metal-organic framework comprises at least one of: aluminum fumarate, MOF-801, MOF-841, including Co₂Cl₂M of BTDD₂Cl₂BTDD, Cr-soc-MOF-1, MIL-101(Cr), CAU-10, alkali metal (Li)⁺，Na⁺) Doped MIL-101(Cr), MOF-303(Al), MOF-802, MOF-805, MOF-806, MOF-808, MOF-812, or mixtures thereof.

65. The apparatus of claim 62 or 63, wherein the water-adsorbing metal-organic framework comprises a plurality of multidentate ligands, wherein at least one ligand is selected from fumarate-or 3, 5-pyrazoledicarboxylic acid (H3PDC) -based ligands.

66. The device of claim 65, wherein the metal ion is selected from Zr⁴⁺、Al³⁺Or a combination thereof.

67. The apparatus of claim 62 or 63, wherein the water-adsorbing metal-organic framework comprises aluminum fumarate.

Technical Field

The present invention generally relates to an apparatus, method and system for capturing aqueous gases such as atmospheric moisture (water content) using water adsorbed metal organic framework composites. In one form, the invention is configured for temperature swing water harnessing. In another form, the invention may be configured for magnetically induced swinging water collection (MFC) using a magnetic framework composite material, which is a composite material formed between a metal organic framework and a magnetic material. However, it is to be understood that the present invention may be used in other water-collecting applications that utilize water-adsorbing metal-organic framework composites.

Background

The following discussion of the background to the invention is intended to facilitate an understanding of the invention. However, it should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was known or part of the common general knowledge as published at the priority date of the application.

In many parts of the world, water can be a scarce resource, particularly in dry or arid environments. However, atmospheric water vapor and water droplets are a natural resource that can be captured to increase the global water supply.

A variety of atmospheric water capture systems have been previously developed that contain sorbent materials that can capture and release water, for example by heating the sorbent materials using solar energy or other external means.

One type of adsorbent material capable of adsorbing water vapor is a Metal Organic Framework (MOF). Many MOFs are known that are capable of adsorbing moisture. These known MOF adsorbents physically adsorb water onto the surfaces within the pores of the MOF.

While MOFs have been considered in many applications, including gas storage, separation and dehumidification, the use of MOFs for water capture has not been proposed until recently.

An example of MOF-based Water capture is taught in Yaghi et al, "Water harvesting from air with metal-organic frames powered by natural basic light," Science 356.6336(2017):430-434(Yaghi 1), and in subsequent publications (which provide further details of the system), "Adsoration-based moved Water harvesting devices for arm markers," Nature communications 9.1(2018):1191(Yaghi 2). The systems described in both papers make use of a porous metal organic framework (microcrystalline powder MOF-801, [ [ Zr ] powder₆O₄(OH)₄(fumarate salt)₆]) Water is captured by vapor adsorption in ambient air with low Relative Humidity (RH) (at 35 ℃, as low as 20% RH). The MOF-801 powder was infiltrated into a porous copper foam brazed on a copper substrate to produce an adsorbed layer with 1.79g of activated MOF-801 with an average filling porosity of-0.85. The geometry of the copper foam is selected to beHas a high substrate area to thickness ratio to reduce parasitic heat loss. Use of less than 1 Sun (1kW m^-2) The non-concentrated solar flux (solar flux) from the MOF, no additional power input is required for producing water at outdoor ambient temperatures. In Yaghi 1, condensation is driven using a condenser coupled to a thermoelectric cooler (using only the cooling side of a thermoelectric "peltier" device) to maintain isobaric conditions of-1.2 kPa (20% RH at 35 ℃, saturation temperature of-10 ℃) in order to condense all water in the desorbed vapor. Such a thermoelectric cooler does not appear to have been used in Yaghi 2. In Yaghi 2, the device reported to capture and deliver water at 20% RH and 35 ℃ at 0.25L kg/MOF/day. It should be noted that Yaghi 2 appears to provide a modified water production result compared to the results published in Yaghi 1.

Despite the promising results taught in Yaghi 1 and Yaghi 2, the use of MOFs infiltrated into conductive substrates still may have low energy conversion efficiency, particularly in the desorption phase using direct solar heating, thereby limiting the amount of possible water production using this system. For example, Yaghi 2 reports that energy efficiency reaches 60% on the gram scale. Significant heat loss is expected in this system due to the energy required to heat the thermal mass of the copper foam substrate.

The limitations of Yaghi 1 and Yaghi 2 suggest that there remains an opportunity to improve the selection and further optimize the use of MOF adsorbents to capture atmospheric water. Accordingly, it would be desirable to provide an improved or alternative water capture method and system that utilizes MOFs to adsorb water from aqueous gases such as the atmosphere and thereby capture water.

Summary of The Invention

The present invention provides an improved and/or alternative MOF-based adsorption apparatus for capturing water from aqueous gases such as air for both commercial and domestic applications.

Water collecting equipment

A first aspect of the invention provides an apparatus for capturing moisture from a water-containing gas. The apparatus comprises:

a housing having an inlet into which aqueous gas (having moisture) may flow;

a water adsorbent enclosed within the housing (i.e., located within the housing), the water adsorbent comprising at least one water-adsorbing metal-organic framework composite capable of adsorbing moisture from an aqueous gas; and

a water desorption apparatus (water desorption arrangement) in contact with and/or surrounding the water adsorbent, the hydrolysis apparatus being selectively operable between (i) a deactivated state and (ii) an activated state in which the apparatus is configured to apply heat, reduced pressure, or a combination thereof to the water adsorbent to desorb water from the water adsorbent.

The present invention provides an apparatus capable of collecting water from an aqueous gas such as ambient air, the apparatus comprising a MOF based composite water adsorbent which can be used to adsorb moisture when a hydrolysis adsorption unit is in a deactivated state, and then selectively operated to desorb water from the water adsorbent by activating a water desorption unit (causing it to operate in an activated state). It is to be understood that "selectively operable" means that a user is able to actively change the condition of the water desorption device from between a deactivated state and an activated state, e.g. switch or trigger such a change of state. Such active changes may be achieved by: the water desorption device is provided with a driving force, such as providing power to power a heater, providing vacuum to reduce pressure, etc., to switch/operate the device in an activated state. Removing the driving force will change the water desorption device to a deactivated state.

Thus, the apparatus is configured to be capable of selectively operating and controlling the adsorption phase and the desorption phase of the water collection cycle of the water adsorbent. Such selective operation advantageously achieves optimization of the efficiency of the hydrolysis absorption unit by using a more efficient water desorption unit to desorb water from the water adsorbent based on the metal organic framework than, for example, using solar energy. In some embodiments, such selective operation may also effect simultaneous condensation of moisture of any product gas stream that includes desorbed water entrained in or otherwise contained in the stream.

The hydrolysis absorption means may take many forms depending on whether heat and/or reduced pressure is used to desorb the adsorbed water from the water adsorbent. In some embodiments, the apparatus is designed for pressure swing adsorption (pressure swing adsorption), wherein desorption is achieved by reducing the pressure, e.g., using a vacuum pump to evacuate gas from around the water adsorbent. Adsorption will typically be carried out at near atmospheric pressure. In other embodiments, temperature swing adsorption (temperature swing adsorption) is performed to achieve water collection. This can be achieved using a direct heating method, or in some cases using magnetic induction swing adsorption (magnetic induction swing adsorption).

It is understood that capturing water from an aqueous gas refers to separating, stripping, or otherwise removing water from the aqueous gas. The aqueous gas may comprise any gas having moisture, such as air (in particular atmospheric air), water-filled nitrogen, water-filled oxygen or the like.

It should also be understood that the aqueous gas may include any number of gases, such as nitrogen, oxygen, or the like. In embodiments, the aqueous gas comprises air, preferably atmospheric air, more preferably ambient air. It is understood that ambient air is the atmosphere at a particular location and in a given environment. It is to be understood that the term "ambient air" is intended to exclude air that has undergone treatment, for example compressed air, degassed air (such as water vapor degassed air), filtered air or the like. Thus, the apparatus may be used to separate and capture moisture from the atmosphere, and thereby capture water.

In case of using an atmosphere, the relative humidity of the atmosphere is preferably between 25% and 100% at 22 ℃, preferably between 40% and 100% at 22 ℃, more preferably between 40% and 80% at 22 ℃. In embodiments, the relative humidity of the atmosphere is between 40% and 60% at 22 ℃, and preferably about 50% at 22 ℃.

The housing of the water device may comprise any suitable container or housing (enclosure) having an inlet. The housing also typically includes an outlet through which outlet gas (exit gas) can flow. The outlet gas typically has a lower water content than the feed aqueous gas due to the adsorption of water by the water adsorbent.

The apparatus may also include one or more doors or other sealing devices mounted on or otherwise closing the inlet and any outlet to enable the housing to form an enclosed environment (or at least a gas-enclosed environment) and thereby enhance desorption and condensation. Any number of sealing doors or sealable opening devices may be used. In some embodiments, the inlet and outlet include at least one fluid seal movable from an open position allowing gas to flow through the inlet and outlet to a closed position in which the inlet and outlet are substantially sealed closed to gas flow. The fluid seal may comprise at least one moveable door, preferably at least one pivotable plate or wing (flap), more preferably at least one louver (louver).

Temperature-changing water collection device

In some embodiments, Temperature swing adsorption water harnessing is achieved using direct conductive heat transfer between a heat source and a water adsorbent. In these embodiments, the hydrolysis suction apparatus comprises at least one heat transfer apparatus in direct thermally conductive contact with the water adsorbent. The heat transfer means is also preferably in heat conducting contact with the heating means. The heat transfer device typically includes one or more heat transfer elements that provide conductive heat transfer from the heating device to the water adsorbent. In some embodiments, the heat transfer device comprises at least one heat transfer element extending from the heating device to the water adsorbent. The heat transfer element may comprise at least one elongated bar, tube, rib (rib) or fin (fin).

A variety of suitable heating devices are available. In an exemplary embodiment, the heating device comprises at least one peltier device. It should be understood that peltier devices are also known as peltier heat pumps, solid state refrigerators, thermoelectric heat pumps, thermoelectric heaters, or thermoelectric coolers. This description will use the term "peltier device" to describe this element of the apparatus. However, it should be understood that each of these alternative terms may be used interchangeably and equally to describe the element of the device.

The peltier device is typically selected to be suitable for providing sufficient energy to desorb water from the shaped water-adsorbing composite. Thus, the peltier device is selected to have a maximum heat flow of at least 50W, preferably at least 75W, more preferably at least 100W, and still more preferably at least 110W. The peltier device is preferably selected to be capable of heating the packed bed to at least 50 ℃, preferably at least 60 ℃, more preferably to at least 65 ℃ and still more preferably to at least 70 ℃. In some embodiments, the peltier device is selected to be capable of heating the packed bed to between 50 ℃ and 90 ℃, preferably between 50 ℃ and 80 ℃, and more preferably between 60 ℃ and 80 ℃. In some embodiments, the peltier device is selected to be capable of heating the packed bed to between 65 ℃ and 85 ℃, preferably between 70 ℃ and 80 ℃, and more preferably about 75 ℃.

The apparatus may further comprise at least one heat transfer device in thermal communication with the peltier device to best utilize the heating side of the peltier device. The water adsorbent is positioned in contact with, e.g., contained within or coated on, at least a portion of the heat transfer device.

The heat transfer device may take a variety of forms, including a variety of heat exchanger configurations. In many embodiments, the heat transfer device comprises a heat sink (i.e., a conductive heat transfer device), preferably a heat sink having an arrangement of plates or fins. In some embodiments, the heat sink device comprises a plurality of spaced apart heat transfer elements. The heat transfer element generally comprises a planar support element, preferably selected from at least one of a plate or a fin.

The shaped water-adsorbing composite may be positioned around, within, or in contact with the heat transfer device in any number of other configurations. In a preferred embodiment, the formed water-adsorbing composite is located within a heat transfer device. In this arrangement, the water adsorbent is contained or mounted as a packed bed between at least two heat transfer elements. The water adsorbent is filled into at least some, preferably all, of the free volume of the heat transfer means.

By driving a fluid stream through and over the water adsorbent, adsorption and desorption from the formed water adsorbent composite may be enhanced. In some embodiments, the apparatus further comprises at least one fluid displacing device to drive a flow of fluid through the packed bed. The fluid displacing means preferably comprises at least one fan. The flow can be driven through the packed bed at a variety of flow rates. To optimize the adsorption and desorption of water, the fluid displacement device preferably produces at least 3m³H, preferably 3m³H to 300m³H, and more preferably 3m³H to 150m³Flow of fluid through the packed bed. It will be appreciated that the amount of air required to flow through the packed bed depends on the level of moisture in the aqueous gas and the efficiency of capture.

The apparatus can also include a condenser system for cooling the product gas stream from the water adsorbent. In some embodiments, the condenser system comprises a cooling device, preferably a cooling trap. In embodiments including a peltier device, the peltier device may also form part of the condenser system. Here, each peltier device has a hot side and a cold side, wherein the hot side of each peltier device is in thermal communication with at least one heat sink and the cold side of each peltier device forms part of the condenser system.

In embodiments, the cold side of each peltier device may also be in thermal communication with at least one heat transfer device, preferably at least one heat sink. The heat transfer means provides additional surface area for contacting the product gas stream to aid in the condensation of moisture therein.

Metal organic framework composite material

The metal-organic framework composite material may be provided in any suitable form in the apparatus. The inventors contemplate that this may be in any number of formulations and forms, including shaped bodies (e.g., pellets or extrudates), coatings, plates, sheets, ribbons, or the like.

In many embodiments, the water adsorbent is a metal organic framework composite comprising:

at least 50 wt% of a water-adsorbing metal organic framework; and

at least 0.1 wt% of a hydrophilic binder.

The metal-organic framework composite may take a variety of forms depending on the desired application, equipment configuration, and adsorption requirements. For example, the metal organic framework composite may comprise a coating applied to the surface of the water desorption device. In other embodiments, the metal organic framework composite comprises a shaped water-adsorbing composite.

In one particular form, the metal organic framework composite comprises a shaped water-adsorbing composite having at least one average dimension greater than 0.5 mm. The formed water-adsorbing composite is formed from a mixture of a water-adsorbing metal-organic framework and a hydrophilic binder, which is preferably optimized for use in a packed bed adsorption system. The combination of a water-adsorbing metal-organic framework and a hydrophilic binder has a surprising synergistic effect, contributing to greater water adsorption compared to the use of other types of binders (e.g. hydrophobic binders).

For atmospheric water collection/capture applications, the inventors have found that three-dimensional shaped bodies of defined composition have excellent water adsorption properties and suitable water adsorption kinetics even at low H₂Partial pressure of O. The formed water adsorbent composites of the present invention also have useful breakthrough test properties for water capture from aqueous gases (water vapor capture) and have been found to have suitable stability when consolidated, formed and heated.

Ideally, the formed water-adsorbing composite should have a good enough affinity for water to adsorb water, but not so high an affinity for water that it requires too much energy to desorb water therefrom. Preferably, for water adsorbed in and/or on the shaped water-adsorbing composite, the heat of adsorption of the water and the adsorbent is in the range from 10kJ/mol MOF to 100kJ/mol MOF.

Optimizing the composition of the formed water-adsorbing composite involves a number of considerations, including:

1. water stability-the components, and in particular MOFs, should be water stable.

2. Reproducibility of adsorption, the shaped water-adsorbing composite should retain adsorption capacity after multiple adsorption/desorption cycles, preferably at least 10 cycles, more preferably at least 100 cycles.

3. The formed water-adsorbing composite and its components should be easy to produce from readily available precursor materials.

4. High water absorption from the air, even at low humidity values.

5. Good affinity for water. The MOF component of the composite should have a good enough affinity for water to enable the MOF to adsorb water, but not so high an affinity for water that it requires too much energy to desorb water from it. The thermodynamics of water adsorption and desorption need to be taken into account here to ensure that the MOF does not require excessive energy (kJ/mol MOF) to desorb water therefrom and thereby adversely affect the energy efficiency of the system.

MOF and other component materials must also comply with regulations for food products for human consumption in relevant countries where the formed water-adsorbing complexes are required for water production for human consumption.

The formed water-adsorbing composite preferably has high water adsorption from aqueous gases such as air, even at low humidity levels. In embodiments, the formed water-adsorbing composite is capable of adsorbing moisture from a moisture-containing gas, preferably air, having a humidity of greater than 20% at 20 ℃, preferably from 20% to 100% at 20 ℃, preferably from 20% to 80% at 20 ℃, and more preferably from 25% to 60% at 22 ℃. In embodiments, the humidity of the aqueous gas is between 25% and 100% at 22 ℃, preferably between 40% and 80% at 22 ℃, preferably between 40% and 60% at 22 ℃, and more preferably about 50% at 22 ℃. In embodiments, the humidity of the aqueous gas is between 20% and 100% at 35 ℃, preferably between 20% and 80% at 35 ℃, preferably between 20% and 60% at 35 ℃, and more preferably about 30% at 22 ℃.

The shaped water-adsorbing composite preferably has a thickness of at least 700m²A/g, and preferably more than 800m²Average surface area in g.

The shaped water adsorbent composite is preferably configured to have dimensions suitable for use in a packed bed adsorption system, wherein a plurality of shaped bodies are packed between two support surfaces at a high packing density of 0.10kg/L to 1.0kg/L, preferably 0.25kg/L to 0.5kg/L, more preferably between 0.25kg/L and 0.35kg/L, and still more preferably about 0.29 kg/L. The dimensions of the formed water-adsorbing composite may be optimized to suit such an application. For use in a packed bed, the formed water adsorbent composite has at least one average dimension greater than 0.5 mm. This ensures that the water adsorbent composite is of sufficient size to allow gas to flow around. For example, fine powders (e.g., having an average particle size of less than 10 microns) generally provide a particle packing that is too dense for use in a packed bed adsorption system. In some embodiments, the formed water-adsorbing composite has at least one average dimension greater than 0.8mm, preferably at least 1mm, preferably at least 1.2mm, and still more preferably at least 1.5 mm. In embodiments, the average width, average depth, and average height of the formed water-adsorbing composite is greater than 0.5mm, and preferably greater than 1 mm.

It is understood that "average size" refers to the average (mean) size of at least one of the width, depth, or height of the formed water-adsorbing composite. Therefore, at least one of the average width, the average depth, or the average height must be greater than a specified size value.

The formed water-adsorbing composite may have any suitable geometry. The shape of the composite body has an effect on the pressure drop of the local fluid flow (in the vicinity of the composite body) and thus on the performance of any packed bed adsorption system. For example, the shaped water-adsorbing composite may comprise pellets (e.g., disk-shaped pellets), pills, spheres, granules, extrudates (e.g., rod-shaped extrudates), honeycombs, meshes, or hollow bodies. In embodiments, the shaped water-adsorbing composite is formed as a three-dimensional body, preferably three-dimensionally shaped. In particular embodiments, the formed water-adsorbing composite comprises an elongate body having a circular or regular polygonal cross-sectional shape. For example, the formed water-adsorbing composite may have a square or triangular cross-sectional shape. In an exemplary form, the formed water-adsorbing composite comprises an elongate body having a triangular cross-sectional shape, preferably an equilateral triangular cross-sectional shape. In one form, the formed water-adsorbing composite has an equilateral triangular cross-section, preferably the sides of the equilateral triangle are at least 1mm in length, preferably between 1.0mm and 1.5mm in length. The length (longitudinal length) of the elongated shaped water-adsorbing composite is preferably from 1mm to 5mm, more preferably from 1mm to 4 mm.

Metal organic framework

The Metal Organic Framework (MOF) constitutes the main adsorption component of the (complex) shaped water adsorption complex. MOF is a crystalline nano-adsorbent with extraordinary porosity. MOFs consist of metal atoms or clusters that are periodically linked by organic molecules to create an array, where each atom forms part of the inner surface. MOFs, which are physical adsorbents, achieve strong adsorption properties through the inner surfaces of the MOF porous structure. The strength of this interaction depends on the capture of H₂Composition of the adsorption surface of MOFs of O molecules. Advantageously, the surface chemistry and structure of MOFs can be tailored for specific applications, where performance criteria such as adsorption/desorption rates, capacity as a function of pressure, and operating temperature may be particularly important.

The formed water-adsorbing composite utilizes the selectivity of MOFs to adsorb water, but not other components in air, such as oxygen and nitrogen. That is, MOF adsorbents are used to capture water from aqueous gases, such as air. For this function, the shaped water-adsorbing composite comprises at least 50 wt% water-adsorbing MOF, preferably at least 70 wt% water-adsorbing MOF, more preferably at least 80 wt% water-adsorbing MOF, still more preferably at least 85 wt% water-adsorbing MOF, and still more preferably at least 90 wt% water-adsorbing MOF.

It is to be understood that "water-adsorbing metal-organic framework" means a water-stable metal-organic framework having a good affinity for water, which adsorbs water even at low humidity values. Preferably, for water adsorbed on the MOF, the heat of adsorption for water is in the range from 10kJ/mol MOF to 100kJ/mol MOF. Ideally, the water adsorbing MOFs should have a good enough affinity for water to enable the MOFs to adsorb water, but not so high an affinity for water that excessive energy is required to desorb water therefrom. Here, the thermodynamics of the adsorption and desorption of water need to be taken into account to ensure that the MOF does not require excessive energy (kJ/mol MOF) to desorb water therefrom and thereby adversely affect the energy efficiency of the system.

Any suitable water-adsorbing metal-organic framework may be used. In some embodiments, the water-adsorbing metal-organic framework comprises at least one of: aluminum fumarate (AlFu), MOF-801, MOF-841, including Co₂Cl₂M of BTDD₂Cl₂BTDD, Cr-soc-MOF-1, MIL-101(Cr), CAU-10, alkali metal (Li)⁺，Na⁺) Doped MIL-101(Cr), MOF-303(Al), MOF-573, MOF-802, MOF-805, MOF-806, MOF-808, MOF-812, or mixtures thereof. In embodiments, the water-adsorbing metal-organic framework is preferably selected from the group consisting of aluminum fumarate, MOF-303, MOF-801, MOF-841, M₂Cl₂BTDD, Cr-soc-MOF-1 or MIL-101 (Cr).

In a particular embodiment, the water-adsorbing metal-organic framework comprises a plurality of polydentate ligands, wherein at least one ligand is selected from fumarate (fumaric acid) or 3, 5-pyrazoledicarboxylic acid (H3PDC) based ligands. In some embodiments, the metal ion is selected from Fe³⁺、Li⁺、Na⁺、Ca²⁺、Zn²⁺、Zr⁴⁺、Al³⁺、K⁺、Mg²⁺、Ti⁴⁺、Cu²⁺、Mn²⁺To Mn⁷⁺、Ag⁺Or a combination thereof. In a preferred embodiment, the metal ion is selected from Zr⁴⁺、Al³⁺Or a combination thereof. Examples include MOF-303[ Al (OH) (C) constructed by linking aluminum (III) ions and 3, 5-pyrazoledicarboxylic acid and AlFu₅H₂O₄N₂)(H₂O)]And MOF-573[ Al (OH) (C)₅H₂O₄N₂)(H₂O)]。

In particular embodiments, the water-adsorbing metal-organic framework comprises a porous aluminum-based metal-organic framework (MOF) comprising inorganic aluminum chains linked via carboxylate groups of a 1H-pyrazole-3, 5-dicarboxylate (HPDC) linker and having the formula: [ Al (OH) (C)₅H₂O₄N₂)(H₂O)]Wherein: each Al (III) ion is capped with four O atoms from four different carboxylate groups and two O atoms from two hydroxyl groups to form AlO₆Octahedral and AlO₆Octahedrally form an angular shared chain, depending on the cis and trans positions of two adjacent bridging hydroxyl groups, the helical chains are in MOF-303 (cis) and MOF-573 (trans) forms, respectively.

In embodiments, the MOF is MOF-303, wherein: the linker further bridges the two strands together, resulting in the formation of a defined diameter ofA 3D skeleton of square one-dimensional channels (which are measured by a maximum-fit sphere); MOF-303 has a topology of xhh; and/or the MOF has a permanent porosity and a Brunauer-Emmett-Teller (BET) surface area of 1380 and 0.55cm³g^-1Pore volume of (a).

In embodiments, the MOF is MOF-573, wherein: the linker further bridges the two strands together, resulting in the formation of a defined diameter ofA 3D skeleton of square one-dimensional channels (which are measured by a maximum-fit sphere); the MOF has a topology of upt; and/or the MOF has a permanent porosity and 980m²g^-1Brunauer-Emmett-Teller (BET) surface area and 0.56cm³g^-1Pore volume of (a).

Water production for human consumption requires the use of materials that comply with the regulations of food products for human consumption in the relevant countries. Thus, in exemplary embodiments, the water-adsorbing MOF comprises aluminum fumarate (AlFu) MOF. The applicant has noted that the advantage of using AlFu is that this MOF is cheap and easy to manufacture.

The water-adsorbing metal-organic framework should preferably exhibit a variety of properties to maximize the functionality of the formed water-adsorbing composite. For example, the water-adsorbing metal-organic framework preferably has at least 700m²A/g, and preferably more than 800m²Average surface area in g. The water-adsorbing metal-organic framework also preferably has a pore size of at least 2nm, preferably greater than 5 nm. The pore size should be sufficient to fit at least with the water molecules therein.

In the present invention, the water-adsorbing MOFs are provided as a powdered material, preferably a powder or a particulate. In embodiments, the water-adsorbing metal-organic framework has a particle size of less than 800 μm, preferably less than 600 μm, and more preferably less than 500 μm. In particular embodiments, the water-adsorbing MOF powder has a particle size of less than 500 μm, preferably less than 300 μm, more preferably less than 212 μm, still more preferably less than 150 μm, and in some embodiments less than 88 μm. It will be appreciated that particle size is typically measured in terms of mesh size through which the particles are sieved. Thus, in embodiments, the water-adsorbing MOF powder has a particle size of less than 60 mesh (250 μm), preferably less than 100 mesh (149 μm), preferably less than 140 mesh (105 μm), and more preferably less than 170 mesh (88 μm). The water-adsorbing MOF powder preferably also has an average particle size between 10 μm and 100 μm, more preferably between 20 μm and 80 μm. In other embodiments, the water-adsorbing MOF powder has an average particle size between 10 μm and 80 μm, and preferably between 20 μm and 60 μm.

Hydrophilic adhesive

If used in a packed bed adsorption system, water adsorption of the MOF powder mixture is not ideal. The individual powders are too densely packed and therefore have too large a pressure drop across the adsorption unit. Therefore, separate powders cannot be used. The inventors have found that water-adsorbing MOFs should be shaped prior to packing into a packed bed water adsorbent system to form shaped water-adsorbing composites, e.g., pellets, for use in a packed bed adsorption system.

The forming process is facilitated by the use of a binder. While shaped composites can be formed without the use of binders, shaped composites containing binders in their composition tend to have greater structural strength and stability when used in packed bed water adsorbent systems. Thus, the formed composite, such as pellets, facilitate continuous operation of the packed bed adsorption system.

The inventors have surprisingly found that a hydrophilic binder must be used to impart optimal water-adsorbing properties to the formed water-adsorbing composite. The inventors have found that non-hydrophilic binders, particularly hydrophobic binders (e.g. cellulose siloxane), greatly affect the water-adsorbing properties of the formed water-adsorbing composite. Thus, the use of a hydrophilic binder is important for optimal moisture capture properties of the packed bed water adsorption system.

A variety of hydrophilic binders can be used for the formed water adsorbent body. The hydrophilic binder may be organic or inorganic and should not block the pores of the water adsorbing MOFs. In some embodiments, the hydrophilic binder comprises a hydrophilic cellulose derivative, preferably an alkyl cellulose derivative, a hydroxyalkyl cellulose derivative, or a carboxyalkyl cellulose derivative. Particularly suitable hydrophilic binders may be selected from at least one of the following: hydroxypropyl cellulose (HPC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose (CMC), or polyvinyl alcohol (PVA). However, it should be understood that other adhesives are possible. In a preferred embodiment, the hydrophilic binder comprises hydroxypropyl cellulose (HPC). It will be appreciated that the additives will depend on the application for which the shaped body is to be used. In the case where water is produced for human consumption, the binder preferably comprises an approved excipient for human consumption. Examples of approved excipients for human consumption include approved excipients for food or pharmaceuticals. Approved food grade or pharmaceutical grade adhesives are preferred.

The formed water-adsorbing composite comprises at least 0.1 wt% hydrophilic binder, and preferably at least 0.2 wt% hydrophilic binder. In embodiments, the formed water-adsorbing composite comprises between 0.2 wt% and 5 wt% of the hydrophilic binder. In some embodiments, the formed water-adsorbing composite may comprise between 0.5 wt% and 3 wt% hydrophilic binder, more preferably between 0.8 wt% and 2 wt% hydrophilic binder, and still more preferably about 1 wt% hydrophilic binder. It is understood that the amount of binder is selected based on the nature and particle size (average size and particle distribution) of the water adsorbing MOF.

Lubricant agent

The formed water-adsorbing composite preferably contains less than 0.5 wt.% of a lubricant, preferably less than 0.1 wt.% of a lubricant. Suitable lubricants include surfactants and salts thereof. Examples of suitable lubricants include magnesium stearate, alumina, sodium oleate, glycerides, diglycerides, triglycerides, fatty acids, oils (including silicone oils and mineral oils), and mixtures thereof. It will be appreciated that the additives will depend on the application for which the shaped body is to be used. In the case of capturing and producing water for human consumption, the lubricant preferably comprises an approved excipient for human consumption. Examples of approved excipients for human consumption include approved excipients for food or pharmaceuticals. Approved food grade or pharmaceutical grade lubricants are preferred. As discussed below, one or more lubricants are added to the mixture to aid in the forming and forming process in preparing the formed water-adsorbing composite.

Packed bed adsorption equipment

In some embodiments, the apparatus comprises a packed bed adsorption system comprising a shaped MOF complex as discussed above. In such embodiments, the water adsorbent is a metal organic framework composite comprising: at least 50 wt% of a water-adsorbing metal organic framework; and at least 0.1 wt% of a hydrophilic binder and having at least one average dimension greater than 0.5 mm. In this regard, the shaped bodies are collected in a packed bed enclosed in a housing. The housing is preferably a fluid tight housing.

The housing preferably includes two spaced apart support membranes configured to allow gas flow through each membrane. A plurality of the shaped water adsorbent composites form a packed bed therebetween and are compressed therebetween. In embodiments, the formed water-adsorbing composite is filled at a density of from 0.10kg/L to 1.0kg/L, preferably 0.25kg/L to 0.5kg/L, and more preferably between 0.25kg/L and 0.35 kg/L. In some embodiments, the formed water adsorbent composite is filled at a density of about 0.25 kg/L. In other embodiments, the formed water adsorbent composite is filled at a density of about 0.29 kg/L. As with any packed bed, it is important that the adsorbent be tightly and substantially uniformly packed throughout the packed bed volume to avoid any short circuits (short circuits) of adsorbent in the packed bed. Any flow that can avoid or follow the route through the shorter/short loop of the packed bed will avoid removal of water from that flow. Short loop flow will adversely affect the energy efficiency and water production rate of the system. The close and uniform filling also ensures a uniform path length to optimize the adsorption performance.

The apparatus may use a low or reduced pressure (sometimes referred to as a vacuum environment) to direct the released water to the condenser. In an embodiment, the pressure is less than 100 mbar, preferably less than 50 mbar, more preferably less than 35 mbar. In other embodiments, the pressure is less than 500 mbar. In other embodiments, the released water is entrained in a gas stream, for example in a stream of aqueous gas or another gas such as an inert gas or other dry gas, and directed to a condenser.

The flow rate of the aqueous gas may also be varied to optimize water adsorption of the packed bed of the formed water adsorption composite. In embodiments, the aqueous gas is fed through the packed bed of formed water-adsorbing composites at the fastest flow rate possible for the device while the water-adsorbing MOFs are still adsorbing water from the aqueous gas. It will be appreciated that the particular flow rate depends on the water content of the water-containing gas, as this determines the mass of water that a particular volume of gas will contain. The water content of the aqueous gas depends on the relative humidity and the temperature and pressure of the aqueous gas. In the case of supplying ambient air to the equipment, a higher flow rate will be required for the lower humidity air to maintain the desired cycle time than for the higher humidity air at the same temperature.

The source of humid air used may be very low relative humidity, simulating the humidity levels found in the most arid regions on earth. In embodiments, the humidity of the air is greater than 20% at 20 ℃, preferably from 20% to 100% at 20 ℃, preferably from 20% to 80% at 20 ℃, and more preferably from 25% to 60% at 22 ℃. In embodiments, the humidity of the air is between 40% and 100% at 22 ℃, preferably between 40% and 80% at 22 ℃, preferably between 40% and 60% at 22 ℃, and more preferably about 50% at 22 ℃. In embodiments, the humidity of the air is between 20% and 100% at 35 ℃, preferably between 20% and 80% at 35 ℃, preferably between 20% and 60% at 35 ℃, and more preferably about 30% at 22 ℃.

The packed bed adsorption system may be configured for magnetically induced oscillatory catchment (adsorption-desorption cycle). Here, the water adsorbent is a magnetic framework composite comprising a mixture of at least 50 wt% of a water adsorbing metal organic framework and from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200nm, and the water desorbing means comprises an Alternating Current (AC) magnetic field generator located in and/or around the water adsorbent and configured to apply an AC magnetic field to the water adsorbent. The water adsorbent preferably comprises a shaped water adsorbent composite in a packed bed in the shell. The formed water-adsorbing composite is preferably filled at a density of from 0.10kg/L to 1.0kg/L, preferably 0.25kg/L to 0.5kg/L, and more preferably between 0.25kg/L and 0.35 kg/L.

The AC magnetic field generator preferably comprises at least one induction coil located within and/or around the packed bed of formed water-adsorbing composite. The AC magnetic field generator is designed to irradiate the packed bed of shaped water-adsorbing composites with an AC magnetic field to release adsorbed water from the packed bed of shaped water-adsorbing composites upon activation.

Magnetic particles

Where induced heat generation is desired for water desorption, the formed water-adsorbing composite may comprise magnetic particles. In these embodiments, the shaped water-adsorbing composite comprises from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm. In some embodiments, the formed water-adsorbing composite may comprise between 0.5 wt% and 7 wt% magnetic particles, and in some embodiments may comprise between 1 wt% to 5 wt% magnetic particles.

The use of such a composite material combines the exceptional adsorption properties of MOFs and enables the use of the high efficiency of magnetic induction heating to desorb water from MOFs. The formed water-adsorbing composite is formed from a Magnetic Framework Composite (MFC), which is a composite combining magnetic particles with MOF crystals. The association of magnetic particles (typically micron-sized or nano-sized magnetic particles) with MOFs allows for the generation of heat when exposed to an Alternating Current (AC) magnetic field. Thus, the MFC can be regenerated using an AC magnetic field as heat is generated in the composite material and this in turn releases the adsorbed fluid from the pores of the MOF portion of the MFC.

This process uses heat generated due to static hysteresis and dynamic core losses of the ferrous/ferromagnetic particles induced by an external AC magnetic field. The heat generation via induction heating takes place remotely and the generated heat is targeted so that the heating process is individual and thus energy-efficient.

The magnetic properties of the magnetic scaffold composite are provided by magnetic particles mixed in the composite. As outlined above, the magnetic particles can be used to generate heat when exposed to an Alternating Current (AC) magnetic field and can thus be used to perform a magnetic induction swing adsorption process on water adsorbed on the water adsorbing MOFs.

The amount of magnetic particles is selected to provide a desired heat generation profile and magnitude when an AC magnetic field is applied. Typically, the amount of magnetic particles in the formed water-adsorbing composite is between 0.2 wt% and 10 wt%. In embodiments, the formed water-adsorbing composite may comprise between 0.5 wt% and 7 wt% magnetic particles, and preferably between 1 wt% and 5 wt% magnetic particles.

A variety of magnetic particles may be used in the shaped adsorbent bodies of the present invention. In embodiments, the magnetic particles comprise ferromagnetic particles, paramagnetic particles, or superparamagnetic particles. In an embodiment, the magnetic particles comprise a metal chalcogenide. Suitable metal chalcogenides include magnetic particles comprising any combination of elemental or ionic forms thereof of M in combination with elemental or elemental forms of at least one of O, S, Se or Te, the M being selected from at least one of: li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi or combinations thereof. In some embodiments, the metal chalcogenide has the formula M_xN_yC_zWherein M and N are selected from at least one of the following: li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, C being selected from at least one of O, S, Se, Te, x being any number from 0 to 10, Y being any number from 0 to 10, and z being any number from 0 to 10. In some embodiments, the metal chalcogenide particles may have a core-shell structure, wherein the core comprises at least one metal chalcogenide as previously described and the shell comprises at least one metal chalcogenide as previously described. In some forms, the core-shell structure may include a plurality of shells. In embodiments, the magnetic particles comprise at least one of: MgFe₂O₄、Fe₃O₄、CoFe₂O₄、NiFe₂O₄Pyridine-2, 6-diamine functionalized SiO₂Pyridine-2, 6-diamine functionalized Fe₃O₄Or C-coated Co.

The magnetic particles may comprise any number of shapes and configurations. In an embodiment, the magnetic particles comprise particles having an irregular shape. In some embodiments, the magnetic particles comprise particles having a regular three-dimensional shape, e.g., spherical, platelet, rod, cylindrical, ovoid, and the like. In some embodiments, the magnetic particles comprise a plurality of magnetic nanospheres. The size of the magnetic particles is typically selected with respect to the desired packed bed application and configuration. Typically, the magnetic particles comprise nanoparticles or microparticles. The magnetic particles have an average particle diameter of less than 200nm, preferably less than 150nm, more preferably between 1nm and 100 nm. In some embodiments, the magnetic particles have an average particle diameter of less than 50 nm. In some embodiments, the magnetic particles have an average particle diameter between 1nm and 200nm, preferably between 5nm and 100nm, more preferably between 5nm and 30nm, and still more preferably between 5nm and 30 nm. In some embodiments, the magnetic particles have an average particle diameter of about 20 nm. It should be noted that the magnetic particles need to be large enough not to contaminate the pores of the water adsorbing the MOFs.

The combination of magnetic particles and MOFs forming a magnetic framework composite material results in an adsorbent that has exceptional adsorption behavior due to the MOFs and high efficiency of induction heating due to the magnetic particles.

Method for capturing moisture from gas containing water

A second aspect of the invention provides a method of capturing moisture from an aqueous gas, the method comprising at least one of the following cycles:

feeding an aqueous gas through an inlet of the housing and past a water adsorbent enclosed within the housing, the water adsorbent comprising at least one water-adsorbing metal-organic framework composite capable of adsorbing moisture from the aqueous gas, such that the water adsorbent adsorbs water from the aqueous gas,

operating at least one water desorption device to change from an inactive state to an active state, to apply heat, to depressurize, or a combination thereof, to the water adsorbent so as to desorb at least a portion of the adsorbed water therefrom into the product fluid stream, and

directing the product fluid stream to a condenser system to separate moisture from the product fluid stream,

wherein the water desorption device is in contact with and/or surrounds the water adsorbent.

The second aspect of the invention also provides a method of capturing moisture from an aqueous gas using an apparatus according to the first aspect of the invention. The method comprises at least one of the following cycles:

feeding an aqueous gas through an inlet of the shell and through the water adsorbent such that the water adsorbent adsorbs water from the aqueous gas, the hydrolysis adsorption unit being in a deactivated state;

operating the at least one water desorption device in an activated state to apply heat, reduced pressure, or a combination thereof to the water adsorbent to desorb at least a portion of the adsorbed water therefrom into the product fluid stream; and

the product fluid stream is directed to a condenser system to separate moisture from the product fluid stream.

In this aspect of the invention, the humidified gas stream is fed through a water adsorbent. After the adsorbent is charged with water vapor, the hydrolysis suction device is activated to heat, depressurize, or a combination. Thus, the water adsorbent is driven to desorb at least a portion of the adsorbed moisture. The desorbed water may be condensed in a condenser system, for example in a cold trap.

It will be appreciated that the apparatus and features thereof used in the method of this second aspect of the invention may also include features previously taught in relation to the first aspect.

The method preferably further comprises the steps of: the inlet and outlet of the housing are closed before operating the at least one water desorption device. This creates a closed, gas-tight environment in the housing, allowing moisture therein to be captured. The relative humidity inside the housing increases to a high value and the water condenses in the condenser system for collection.

It is to be understood that the method is a cyclic method in which the steps of adsorbing water in a water adsorbent, releasing the adsorbed water by operation of a water desorption device, and condensing the water are performed in repeated cycles so as to continuously produce water. The cycle time is typically dependent on the configuration of the water adsorbent and adsorption system, the amount of water adsorbing MOF, breakthrough point, saturation point, temperature, pressure, and other process conditions. In some embodiments, one cycle of the process has a duration of less than 10 hours, preferably less than 8 hours, more preferably less than 7 hours, and more preferably 6 hours or less. In other embodiments, the cycle time of the method steps lasts about 30 minutes. However, other cycle times between 10 minutes and 10 hours may also be possible depending on the configuration of the device.

As mentioned above, the apparatus of the present invention may be configured for temperature swing water collection (adsorption-desorption cycle). In these systems, a heat source is required to heat the packed bed of formed water adsorbent composite. In some embodiments, operating the at least one water desorption device comprises operating the at least one peltier device to heat the water adsorbent so as to desorb at least a portion of the adsorbed water therefrom into the product fluid stream. The at least one peltier device may also form part of a condenser system configured to cool the product fluid stream. This arrangement advantageously utilizes both the heating side and the cooling side of the one or more peltier devices used.

In other embodiments, the apparatus of the present invention may be configured for magnetically induced oscillatory catchment. Here, the step of operating the at least one water-desorbing means comprises applying an alternating magnetic field to the packed bed of the shaped water-adsorbing composite to generate heat within the shaped water-adsorbing composite to release at least a portion of the adsorbed water therefrom into the product fluid stream, the shaped water-adsorbing composite comprising at least 50 wt% of the water-adsorbing metal-organic framework; and at least 0.1 wt% of a hydrophilic binder and from 0.2 to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm.

The shaped water-adsorbing composite in the process is subjected to magnetically induced vacuum swing adsorption to capture water from an aqueous gas fed into a packed bed of the shaped water-adsorbing composite. The application of the AC magnetic field depends on the amount of water adsorbed in the shaped water adsorption complex in the packed bed. Thus, the method takes advantage of the high energy conversion efficiency of magnetic induction heating. In embodiments, the apparatus and method have an energy conversion efficiency of greater than 90%, preferably greater than 95%, and in some embodiments up to 98% energy conversion efficiency is achieved. Furthermore, the use of rapid heating by magnetic induction heating enables short cycle times to be achieved. In embodiments, the process has a cycle time of less than 2 hours, preferably less than 1 hour.

Adsorption is a short process. The amount of material adsorbed within the bed depends on both location and time. Over time, the active adsorption zone of the packed bed moves away from the inlet and through the bed. The mass transfer zone moves through the bed until it "breaks through". The fluid flowing out of the bed will have little or no solute remaining-at least until a large portion of the bed becomes saturated. Breakthrough occurs when the concentration of fluid exiting the bed spikes (spikes) as non-adsorbed solutes begin to appear. The bed still adsorbs water, albeit at a slower rate than before the breakthrough point, until the bed becomes saturated and is no longer able to adsorb water, which is defined as the "saturation point" of the bed. Thus, in terms of the saturation point of the packed bed, the alternating magnetic field is preferably applied when the packed bed has adsorbed water equal to at least 75% of the saturation point of the packed bed, preferably at least 80%, more preferably at least 90% of the saturation point of the packed bed. This ensures that the adsorption capacity of the packed bed is fully utilized, but allows water to be released before the packed bed is fully saturated.

The AC magnetic field is applied for a period of time necessary to substantially release the water adsorbed on the shaped water adsorption complex in the packed bed. The application time depends on the shape, size and configuration of the packed bed, the shape, size and configuration of the AC magnetic field generator, the strength of the applied magnetic field and the amount of magnetic particles in the formed water adsorption complex. In some embodiments, the AC magnetic field is applied for at least 1 second. In an embodiment, the AC magnetic field is applied for between 1 and 120 seconds, preferably between 1 and 60 seconds, more preferably from 10 to 30 seconds.

The strength of the magnetic field applied to the packed bed of formed water adsorbent composites is generally tailored to the shape, size and configuration of the packed bed. In embodiments, the magnetic field strength is at least 10mT, preferably at least 12mT, preferably about 12.6 mT. It will be appreciated, however, that the magnetic field strength selected will depend on the particular application and is generally selected to provide the lowest power consumption, and therefore the lowest magnetic field strength, for the greatest amount of heat required to desorb water from the water adsorbing MOFs. The frequency of the AC magnetic field may be selected to provide maximum heating. In an embodiment, the frequency of the AC magnetic field is between 200kHz and 300kHz, preferably between 250kHz and 280kHz, and more preferably from 260kHz to 270 kHz. Likewise, the frequency may be selected for a particular application and customized/optimized to provide maximum heating for the lowest power consumption.

Likewise, it is understood that the aqueous gas may include a variety of gases, such as nitrogen, oxygen, or the like. In embodiments, the aqueous gas comprises air, preferably atmospheric air, more preferably ambient air. Thus, the method may be used to separate and capture moisture from the atmosphere, and thereby capture water.

The condenser system is used to separate the moisture of the product fluid stream (typically a gas with entrained water vapor) to produce water. It should be understood that a variety of condenser arrangements are possible and selected to meet the particular requirements of the system being designed. The condenser is used to convert water vapor in the product fluid stream to liquid water. In some embodiments, the condenser comprises a heat transfer/cooling device, such as a cooling trap, an air coil, a surface condenser, or another heat exchange device.

In some embodiments, the metal organic framework adsorbent may be activated prior to use (i.e., for moisture adsorption) by heating the composite and passing a dry nitrogen stream through the (feed) column to trigger the metal organic framework adsorbent. Where the water adsorbent comprises a composite comprising magnetic particles, heating may be achieved by an alternating magnetic field. The activation of the material is carried out until the humidity of the outgoing air flow is zero.

Overall, the method and related apparatus have a water generation capacity of at least 2.8L/kg of MOF, more preferably at least 3.5L/kg of MOF, still more preferably at least 4L/kg of MOF, and in some embodiments about 4.1L/kg of MOF at 20% RH and 35 ℃. Typical energy consumption is between 10kWh/L of produced water and 15kWh/L of produced water, typically around 12kWh/L of produced water.

Temperature swing apparatus for capturing water from water-containing gas

A third aspect of the invention provides apparatus for capturing moisture from an aqueous gas, the apparatus comprising:

at least one heat transfer device in contact with a packed bed of a shaped water-adsorbing composite having at least one average dimension greater than 0.5mm and comprising at least 50 wt% of a water-adsorbing metal-organic framework; and at least 0.1 wt% of a hydrophilic binder; and

at least one Peltier device in thermal communication with each heat transfer device, each Peltier device configured to heat the shaped water-adsorbing composite to desorb water therefrom for entrainment into a product fluid stream,

wherein the at least one peltier device also forms part of a condenser system for cooling the product fluid stream from the packed bed of the shaped water-adsorbing composite.

This third aspect of the invention provides a water capture apparatus comprising a shaped water-adsorbing composite that uses temperature-swing induction heating to desorb water adsorbed within and on a shaped body. In this regard, the shaped bodies are collected in a packed bed closed in contact with a heat sink. The apparatus further comprises a peltier device configured to heat the packed bed of the shaped water-adsorbing composite to release adsorbed water from the packed bed of the shaped water-adsorbing composite upon activation. The peltier device is also configured to provide a cooling function to drive condensation of the fluid stream desorbed from the shaped water-adsorption complex of the packed bed.

As described above with respect to the first aspect, the peltier device is preferably selected to be suitable for providing sufficient energy to desorb water from the shaped water-adsorbing composite. Thus, the peltier device is selected to have a maximum heat flow of at least 50W, preferably at least 75W, more preferably at least 100W, and still more preferably at least 110W. Furthermore, the peltier device may be selected to be capable of heating the packed bed to at least 50 ℃, preferably at least 60 ℃, more preferably at least 65 ℃ and more preferably at least 70 ℃. In some embodiments, the peltier device is selected to be capable of heating the packed bed to between 50 ℃ and 90 ℃, preferably between 50 ℃ and 80 ℃, more preferably between 50 ℃ and 80 ℃, still more preferably between 65 ℃ and 85 ℃. In some embodiments, the peltier device is selected to be capable of heating the packed bed to between 70 ℃ and 80 ℃, and preferably about 75 ℃.

The shaped water-adsorbing composite may be positioned around, within, or in contact with the heat transfer device in any number of other configurations. In a preferred embodiment, the formed water-adsorbing composite is located within a heat transfer device.

Likewise, the heat transfer device may take a variety of forms, including a variety of heat exchanger configurations. In many embodiments, the heat transfer device comprises a heat sink (i.e., a conductive heat transfer device), preferably a heat sink having an arrangement of plates or fins. In some embodiments, the heat sink device comprises a plurality of spaced apart heat transfer elements. In this arrangement, the formed water-adsorbing composite is installed as a packed bed between at least two heat transfer elements. The heat transfer element typically comprises at least one of a plate or a fin.

By driving a fluid stream through and past the shaped water-adsorbing composite, adsorption and desorption from the shaped water-adsorbing composite may be enhanced. In some embodiments, the apparatus further comprises at least one fluid displacing device to drive a flow of fluid through the packed bed. The fluid displacing means preferably comprises at least one fan. The flow can be driven through the packed bed at a variety of flow rates. To optimize the adsorption and desorption of water, the fluid displacement device preferably produces at least 3m³H, preferably 3m³H to 300m³H, and more preferably 3m³H to 150m³Flow through the packed bed. It will be appreciated that the amount of air required to flow through the packed bed depends on the level of moisture in the aqueous gas and the efficiency of capture.

When in operation, each peltier device forms a hot side and a cold side (as described in more detail in the detailed description). In such an arrangement, the hot side of each peltier device is preferably in thermal communication with at least one heat sink, and the cold side of each peltier device forms part of the condenser system.

The condenser system may further comprise a heat transfer device to facilitate heat transfer from the ambient gas to the cold side of the peltier device. In an embodiment, the cold side of each peltier device is in thermal communication with at least one heat transfer device. Like the hot side, the heat transfer means preferably comprises a heat sink (conductive heat transfer means), and more preferably a heat sink having a plate or fin arrangement.

A fourth aspect of the invention provides a method of capturing moisture from a water-containing gas using an apparatus according to the fourth aspect of the invention. The method comprises at least one of the following cycles:

feeding an aqueous gas through a packed bed of shaped water adsorption complexes of the apparatus such that the shaped water adsorption complexes adsorb water from the aqueous gas;

operating at least one peltier device to heat the formed water adsorption complex so as to release at least a portion of the adsorbed water therefrom into the product fluid stream; and

the product fluid stream is directed to a condenser system to separate moisture from the product fluid stream.

It will be appreciated that operating at least one peltier device to heat the shaped water adsorbing composite generates heat through the peltier device from its cold side to its hot side. Thus, the operation of at least one peltier device also causes the cold side of each peltier device to operate (turn on) and thereby start the operation of the condenser system via the cold side of the peltier device forming part of the condenser system.

It is to be understood that the process is a cyclic process wherein the steps of adsorbing water in the shaped water-adsorbing composite, releasing the adsorbed water by heating from at least one peltier device, and condensing the water are performed in repeated cycles so as to continuously produce water. Cycle times are generally dependent upon the configuration of the packed bed and adsorption system, the amount of water adsorption complex formed, the depth of the packed bed, the breakthrough point, the saturation point, and the characteristics of the particular packed bed, temperature, pressure, heat sink configuration, peltier device, and other process conditions. In some embodiments, the cycle time of the method steps lasts about 6 hours. However, other cycle times between 1 hour and 24 hours may also be possible depending on the configuration of the equipment and packed bed and the process conditions.

The condenser system is used to separate the moisture of the product fluid stream (typically a gas with entrained water vapor) to produce water. It should be understood that a variety of condenser arrangements are possible and selected to meet the particular requirements of the designed system. The condenser is used to convert water vapor in the product fluid stream to liquid water. In some embodiments, the condenser comprises a heat transfer/cooling device, such as a cooling trap, an air coil, a surface condenser, or another heat exchange device.

Magnetic pendulum device for capturing water from gas containing water

A fifth aspect of the invention provides an apparatus for capturing moisture from an aqueous gas, the apparatus comprising:

a housing containing a packed bed of shaped water-adsorbing composite in the housing, the shaped water-adsorbing composite having at least one average dimension greater than 0.5mm and comprising at least 50 wt% of a water-adsorbing metal-organic framework; at least 0.1 wt% of a hydrophilic binder and from 0.2 to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm; and

an Alternating Current (AC) magnetic field generator positioned within and/or about the packed bed of the shaped water-adsorbing composite configured to apply an AC magnetic field to the packed bed of the shaped water-adsorbing composite.

This fifth aspect of the invention provides a water capture apparatus comprising a shaped body that uses magnetic oscillatory induction heating to desorb water adsorbed within and on the shaped body. In this regard, the shaped bodies are collected in a packed bed enclosed in a housing. The housing is preferably a fluid tight housing. The apparatus further includes an AC magnetic field generator configured to irradiate the packed bed of shaped water-adsorption complexes with an AC magnetic field to release adsorbed water from the packed bed of shaped water-adsorption complexes upon activation. The apparatus is configured to enable the shaped water-adsorbing composite to undergo magnetically induced swing adsorption to capture water from an aqueous gas fed into a packed bed of the shaped water-adsorbing composite.

Any AC magnetic field generator capable of applying a localized AC magnetic field to a packed bed of shaped water adsorption complexes may be used. In some embodiments, the AC magnetic field generator comprises at least one induction coil positioned within and/or around the packed bed of formed water-adsorbing composites. Preferably, one or more induction coils are embedded in and surrounded by the shaped water adsorbent composite in the packed bed so as to use the entire magnetic field generated by the one or more induction coils. In some embodiments, the one or more induction coils are configured to be located within the central section of the packed bed, occupying from 50% to 90%, preferably from 70% to 80%, of the axial height (depth) of the packed bed.

The housing has a fluid inlet and a fluid outlet through which a fluid, preferably a moisture-containing gas and a product fluid, is configured to flow. The housing may have any suitable configuration. In some embodiments, the housing comprises a container or canister, e.g., a substantially cylindrical container or canister. The housing is preferably fluid tight, with only fluid entering and exiting through the inlet and outlet of the housing. In other embodiments, the housing comprises a flat, high surface area container. It should be understood that a variety of container and can shapes and configurations may be used. The housing may be replaceable or fixedly mounted in the system.

A plurality of the shaped water-adsorbing composites are preferably arranged in a housing in a packed bed system. The housing may comprise two spaced apart support membranes configured to allow gas to flow through each membrane, a plurality of said shaped water-adsorbing composites forming a packed bed therebetween and preferably being compressed therebetween. The apparatus of the fifth aspect may further comprise a condenser system for cooling the fluid stream from the packed bed of shaped water-adsorbing composite. A variety of condensers may be used. In an embodiment, the condenser comprises a cooling device, such as a cooling trap.

The inventors have found that drinking water can be produced rapidly using the apparatus of this aspect of the invention. The apparatus utilizes a packed bed of shaped water adsorption complexes of the first aspect of the invention in a magnetically induced vacuum swing adsorption system to separate and thereby capture water from an aqueous gas, such as humid air, and release and collect the captured contents using a condenser.

A sixth aspect of the invention provides a method of capturing moisture from an aqueous gas using an apparatus according to the fifth aspect of the invention, comprising at least one of the following cycles (including the steps of):

feeding an aqueous gas through a packed bed of shaped water adsorption complexes of the apparatus such that the shaped water adsorption complexes adsorb water from the aqueous gas;

applying an ac magnetic field to the shaped water-adsorbing composite using an ac magnetic field generator of the apparatus, thereby generating heat within the shaped water-adsorbing composite to release at least a portion of the adsorbed water therefrom into the product fluid stream; and

the product fluid stream is directed to a condenser to separate moisture from the product fluid stream.

In this sixth aspect of the invention, the humidified gas stream is fed through a packed adsorbent column. After the adsorbent is charged with water vapor, an alternating magnetic field is applied. Thus, the pellets begin to warm rapidly, forcing the water to be released. The desorbed water is condensed in a condenser, for example, in a cold trap. Thus, the method utilizes the high energy conversion efficiency of magnetic induction heating. In embodiments, the apparatus and method have an energy conversion efficiency of greater than 90%, preferably greater than 95%, and in some embodiments up to 98% energy conversion efficiency is achieved. Furthermore, the use of rapid heating by magnetic induction heating enables short cycle times to be achieved.

It is to be understood that the process is a cyclic process in which the steps of adsorbing water in the formed water-adsorbing composite, releasing the adsorbed water by applying an AC magnetic field, and condensing the water are performed in repeated cycles to continuously produce water. Cycle time generally depends on the configuration of the packed bed and adsorption system, the amount of water adsorption complex formed, the depth of the packed bed, breakthrough point, saturation point, and the characteristics of the particular packed bed, temperature, pressure, and other process conditions. In some embodiments, the cycle time of the method steps lasts about 30 minutes. However, other cycle times between 10 minutes and 2 hours may also be possible depending on the configuration of the equipment and the packed bed and the process conditions.

Method of forming shaped water-adsorbing composites

The present invention may also provide a method of forming a shaped water-adsorbing composite for use in the adsorption system of the first aspect. The method comprises the following steps:

preparing a composite powder mixture comprising at least 50 wt% of a water-adsorbing metal-organic framework; at least 0.1 wt% of a hydrophilic binder; and optionally 0.2 to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm;

preparing a composite paste comprising a mixture of a composite powder mixture and a solvent;

forming the composite paste into a shaped body having at least one average size greater than 0.5 mm; and

heating the shaped body to substantially remove the solvent from the shaped body,

thereby producing a shaped water adsorption composite for use in a packed bed adsorption system.

This aspect of the invention provides a method of forming a shaped water-adsorbing composite for use in various embodiments of the invention. In this method, a composite powder mixture (typically a powdered material) comprising a powder mixture of a metal-organic framework and a hydrophilic binder is formed into a paste using a solvent, which paste can then be shaped into the desired shaped body, for example by an extrusion or granulation process.

The solvent used to form the shaped body can be any suitable solvent that has good interaction with the components of the composite powder mixture. Suitable solvents are preferably selected from non-basic polar solvents and/or non-self-ionizing polar solvents. The solvent preferably comprises an alcohol, such as methanol, ethanol, C2-C9 alcohol (including branched isomers thereof); or water, more preferably deionized water.

A hydrophilic binder and a liquid solvent are added to the composite powder mixture to help form a suitable paste for the forming process. It is understood that the composite paste comprises a thick, soft, moist mixture. The paste preferably has sufficient viscosity to retain shape when formed into the desired configuration in the forming/shaping step. An amount of solvent is typically mixed with the composite powder material (powdered material, preferably powder or granules) to provide a suitable paste consistency for a forming process such as extrusion or granulation.

It is also important to understand that the shaped bodies preferably comprise water adsorbing MOFs and hydrophilic binders. The solvent is used purely to form a paste, and the solvent is evaporated or otherwise removed from the shaped composite material during the heat treatment step.

Magnetic particles may also be included in the formed shaped composite material. In these embodiments, the composite powder mixture further comprises from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm.

The composite paste may be formed into a shaped body using a variety of processes. In embodiments, forming the composite paste into a shaped body comprises at least one of: the composite paste is extruded, pelletized or molded into the desired three-dimensional configuration. Preferred methods include rod extrusion (rod extrusion) or tableting. Where the shaped body is formed by extrusion or similar process such that the composite paste is extruded into a long body, the body is preferably subsequently divided longitudinally, typically into lengths suitable for use in a packed bed adsorption system. Preferably, after extrusion, the extruded elongate body is allowed to dry (e.g. air dry) for a period of time before being longitudinally divided. The drying time may vary, but is typically at least 10 minutes. The extrudate is then cut into shaped bodies, preferably pellets, of 3mm to 5mm length.

The shaping step may be carried out in the presence of a lubricant and/or other additional substance that stabilizes the material to be agglomerated. Suitable lubricants include surfactants and salts thereof. Examples of suitable lubricants include magnesium stearate, alumina, sodium oleate, glycerides, diglycerides, triglycerides, fatty acids, oils (including silicone oils and mineral oils), and mixtures thereof. It will be appreciated that the additives will depend on the application for which the shaped body is to be used. In the case where water is produced for human consumption, the lubricant preferably comprises an approved excipient for human consumption. Examples of approved excipients for human consumption include approved excipients for food or pharmaceuticals. Approved food grade or pharmaceutical grade lubricants are preferred. As discussed below, when preparing the shaped bodies, a lubricant is added to the mixture to aid in the shaping and forming process. In some embodiments, the lubricant may be mixed in the powder mixture with a binder to form a portion of the powder mixture. In other embodiments, the lubricant is applied to the surface of a forming device, such as an extruder or pelletizer, to lubricate only the outer surface. The resulting shaped water-adsorbing composite preferably contains less than 0.5 wt.% lubricant, preferably less than 0.1 wt.% lubricant.

The one or more shaped bodies are preferably formed in a size suitable for a packed bed adsorption system, wherein a plurality of shaped bodies are packed between two support surfaces at a high packing density of 0.10kg/L to 0.5kg/L, preferably 0.25kg/L to 0.4 kg/L. The dimensions of the shaped body can be optimized to suit this application. When used in a packed bed adsorption system, the formed water adsorption composite has at least one average dimension greater than 0.5 mm. This ensures that the water adsorbent composite is of sufficient size to allow gas to flow around. For example, a fine powder (e.g., having an average particle size of less than 10 microns) provides a packing that is too dense for a packed bed used in a packed bed adsorption system. In some embodiments, the shaped bodies have at least one average dimension greater than 0.8mm, preferably at least 1mm, preferably at least 1.2mm, and still more preferably at least 1.5 mm. Preferably, each of the average width, average depth and average height of the shaped bodies is greater than 0.5mm, and preferably greater than 1 mm.

The shaped body may be formed to have any suitable geometry. The shape of the shaped water adsorbent composite has an effect on the pressure drop of the local fluid stream (in the vicinity of the composite) and thus on the performance of any packed bed adsorption system. For example, the shaped bodies can include pellets (e.g., disk-shaped pellets), pills, spheres, granules, extrudates (e.g., rod-shaped extrudates), honeycombs, meshes, or hollow bodies. In embodiments, the shaped body is three-dimensional, preferably three-dimensionally shaped. In a particular embodiment, the shaped body comprises an elongated body having a circular or regular polygonal cross-sectional shape. In a preferred embodiment, the shaped body comprises a triangular cross-sectional shape, and more preferably an equilateral triangular cross-sectional shape. For example, the shaped body may have a square or triangular cross-sectional shape. In one form, the shaped body has an equilateral triangular cross-section, preferably the sides of the equilateral triangle are at least 1mm in length, preferably between 1.0mm and 1.5mm in length. The length (longitudinal length) of the elongated shaped body is preferably from 1mm to 5mm, more preferably from 1mm to 4 mm. In some embodiments, the elongated shaped body has a length of 3mm to 5 mm.

The heating step is preferably carried out for a sufficient time to remove the solvent from the shaped body. The heating step is preferably carried out at a temperature between 80 ℃ and 150 ℃, preferably between 90 ℃ and 120 ℃. The heating step may be carried out for at least 1 hour, preferably at least 2 hours, more preferably at least 5 hours, still more preferably at least 8 hours, and still more preferably at least 10 hours. Similarly, the pressure is selected to facilitate solvent removal. In an embodiment, the pressure is less than 100 mbar, preferably less than 50 mbar, more preferably less than 35 mbar. In other embodiments, the pressure is less than 500 mbar. In some embodiments, the heating step is performed in an inert gas atmosphere, such as nitrogen or argon.

The heating step may include an additional activation step in which one or more of the shaped adsorbent bodies are dried at elevated temperature to ensure that the pores of the water adsorbing MOF are free of moisture or solvent. In some embodiments, the activating heating step comprises heating the shaped adsorbent body to at least 120 ℃, preferably between 120 ℃ and 150 ℃, for at least 5 hours, preferably at least 6 hours, more preferably from 6 hours to 10 hours, and more preferably from 6 hours to 8 hours. The activation heating step is preferably carried out at reduced pressure below 200 mbar, preferably below 100 mbar, and more preferably below 50 mbar. In some embodiments, the shaped adsorbent is heated to a temperature of 130 ℃ at a pressure below 200 mbar, preferably below 100 mbar, more preferably below 50 mbar, to activate MOF for 6 to 8 hours.

In other embodiments, the shaped adsorbents may be activated by triggering them with an alternating magnetic field within a flow of inert gas (e.g., a flow of dry nitrogen). Activation of the shaped adsorbent body may be carried out until the humidity of the outgoing air stream is zero.

After heating, the material is preferably cooled to at most 80 ℃, preferably at most 60 ℃ under reduced pressure of at most 500 mbar, preferably at most 100 mbar.

It is to be understood that the water produced by the apparatus and method according to embodiments of the present invention may be used for any purpose, including but not limited to:

water as a substrate for energy production or chemical synthesis, etc.;

water for special purposes, such as ultrapure water for medical use or laboratory use, and the like;

water for the defense sector or the medical sector;

water for industrial applications such as agriculture, irrigation, fire extinguishing, etc.;

water for consumption, such as domestic water, bottled water, food process water, and the like.

Brief Description of Drawings

The invention will now be described with reference to the figures in the accompanying drawings, which illustrate particularly preferred embodiments of the invention, and in which:

FIG. 1A is a schematic view of a magnetically induced oscillating device for capturing moisture from an aqueous gas, according to one embodiment of the present invention.

FIG. 1B is a schematic view of a magnetically induced oscillating device for capturing moisture from an aqueous gas, according to another embodiment of the present invention.

Fig. 1C is a schematic view of a temperature change device for capturing moisture from an aqueous gas, including a heat sink (CPU cooler) and a peltier device, according to one embodiment of the present invention.

Fig. 1D is a photograph of an experimental temperature change device for capturing moisture from an aqueous gas, including a heat sink (CPU cooler) and a peltier device, according to one embodiment of the present invention.

FIG. 1E provides the thermal cycle water collection apparatus shown in FIG. 1C during (A) the adsorption phase; and (B) a schematic of the operation when operating during the desorption phase.

FIG. 2A is a photograph of an experimental setup for aluminum fumarate synthesis.

Figure 2B is a photograph of aluminum fumarate produced after a washing procedure.

Fig. 2C provides a schematic illustration of a shaped adsorbent body according to one embodiment of the present invention for use in a packed bed of the apparatus shown in fig. 1A-1D.

FIG. 3A is a photograph of a manual extruder and triangular nozzle used to produce shaped aluminum fumarate composite pellets.

Fig. 3B provides a schematic of a pellet formation process.

FIG. 4 is a photograph showing aluminum fumarate and aluminum fumarate composite pellets produced, wherein (A) pure MOF; (B)1 wt% binder; (C)1 wt% MNP; (D)3 wt% MNP; and (E)5 wt% MNP.

Fig. 5 is a schematic diagram of an experimental setup for induction heating experiments.

Fig. 6 is a schematic diagram of an experimental magnetically induced oscillatory water capture device.

FIG. 7 provides PXRD patterns for aluminum fumarate, simulated aluminum fumarate, and aluminum fumarate with 1 wt% binder (batch I).

Figure 8 provides PXRD patterns for different aluminum fumarate magnetic composites, aluminum fumarate with 1 wt% binder (batch I), and magnesium ferrite for reference.

Fig. 9 provides PXRD patterns for aluminum fumarate magnetic composites, aluminum fumarate (batch II), and magnesium ferrite for reference.

FIG. 10 provides an SEM image of an aluminum fumarate metal organic framework (batch II). Magnification ratio: 10000 times.

Fig. 11 provides SEM images of magnesium ferrite nanoparticles. Magnification ratio: 10000 times.

Fig. 12 provides an SEM image of an aluminum fumarate magnetic backbone composite (batch II) at 10000 x magnification. The circled portion marked a indicates the location of the magnesium ferrite nanoparticles in the composite.

Figure 13 provides the average BET surface area of aluminum fumarate composites as a function of magnetic nanoparticle loading.

FIG. 14 provides a graph of the pore size distribution of aluminum fumarate MOF pellets (batch I).

FIG. 15 provides a nitrogen isotherm for aluminum fumarate pellets.

Fig. 16 provides a plot of the pore size distribution of an aluminum fumarate composite pellet comprising: (a)1 wt% binder; (b)1 wt% MNP; (c)3 wt% MNP; (d)5 wt% MNP.

Figure 17 provides water vapor adsorption isotherms for aluminum fumarate batch I and aluminum fumarate batch I composite pellets collected at room temperature.

Figure 18 provides water vapor adsorption isotherms for aluminum fumarate batch II and aluminum fumarate batch II composite pellets collected at room temperature.

Fig. 19 provides a graph of the initial heating rate of induction heating of aluminum fumarate magnetic matrix composites with different concentrations of MNP. The field strength is 12.6 mT.

Fig. 20 provides a graph of the efficiency of induction heating of aluminum fumarate magnetic scaffold composites with different MNP loadings. The field strength is 12.6 mT.

Fig. 21 provides a graph of normalized relative humidity versus time for adsorption of water vapor from a nitrogen stream.

Fig. 22 provides a graph of the temperature profile of an aluminum fumarate composite during adsorption of moisture.

FIG. 23 provides a graph of normalized relative humidity versus time for the effluent stream during regeneration.

FIG. 24 provides a graph of the temperature profile of an aluminum fumarate composite during regeneration of water vapor.

Figure 25 provides a comparison of (a) first lots of AlFu (aluminum (I) fumarate); (B) pellets comprising aluminum fumarate (I) and a cellulosic siloxane binder; (C) a second batch of AlFu (aluminum (II) fumarate); and (D) a plot of the water vapor absorption isotherm of pellets comprising aluminum (II) fumarate and hydroxypropyl cellulose binder.

Fig. 26 illustrates the setup of a testing apparatus (testing rig) for the temperature changing water collecting apparatus shown in fig. 1C and 1D, including a power source and a measuring device.

Fig. 27 illustrates FTIR plots for aluminum fumarate with 1 wt% binder after the granulation process for each of three batches (batch _01, batch _02, and batch _03), and for pure aluminum fumarate (pristine aluminum fumarate).

Figure 28 illustrates PXRD patterns of pure aluminum fumarate and all three extrudates with 1 wt% binder after the granulation process. The simulated plots were used for comparison.

FIG. 29 illustrates the water absorption isotherm (squares) at 26 ℃ of aluminum fumarate pellets produced in this work (pellet _02), as well as literature data for aluminum fumarate from Teo et al [28] (diamonds).

FIG. 30 illustrates a graph having 8.85gm^-3Mass recording of the sorption phase of humidity. This data was used to calculate the theoretical adsorption time for all water collection cycles.

Fig. 31 illustrates the optimization of the condensation time of the water collection device, which plots the space time yield and specific energy over different condensation times corresponding to the water collection cycles 12, 14, 15, 16 and 17.

Fig. 32 illustrates the optimization of the desorption temperature of the water collecting device, which plots the space time yield and the specific energy at different desorption temperatures corresponding to the water collecting cycles 16, 18, 19 and 20.

Fig. 33 illustrates the adsorbed temperature and relative humidity of the water collection cycle 16.

Fig. 34 illustrates the temperature in the water collection device during the desorption phase of the water collection cycle 16.

Fig. 35 illustrates the relative humidity, dew point and condenser temperature in the water collection device during the desorption phase of the water collection cycle 16.

Fig. 36 illustrates the adsorbed temperature and relative humidity of the water collection cycle 24.

Fig. 37 illustrates the temperature in the water collection device during the desorption phase of the water collection cycle 24.

Fig. 38 illustrates the relative humidity, dew point and condenser temperature in the water collection device during the desorption phase of the water collection cycle 24.

Fig. 39 illustrates the temperature and relative humidity of adsorption of the water collection cycle 22.

Fig. 40 provides two views of a prototype water capture apparatus using a temperature swing water collection embodiment, showing (a) an outer housing; and (B) interior components, including a blind system.

Detailed Description

The present invention provides an apparatus that provides selective control of the adsorption and desorption phases of a water uptake cycle of MOF-based water adsorbents. The apparatus includes a water desorption device that allows the MOF based water adsorbent to adsorb water when in a deactivated state, and then applies desorption conditions to the water adsorbent to desorb water from the water adsorbent when in an activated state. This selective operation of the water desorption device between the deactivated state and the activated state enables the use of a more efficient energy desorption device for desorbing water from the metal organic framework based water adsorbent compared to, for example, utilizing solar energy, to optimize the efficiency of the water desorption device, and in some embodiments, to simultaneously condense moisture from any product gas stream.

Adsorption equipment

The hydrolysis absorption means may take many forms depending on whether heat and/or reduced pressure is used to desorb the adsorbed water from the water adsorbent. In some embodiments, the apparatus is designed for pressure swing adsorption, wherein desorption is achieved by reducing the pressure, e.g., using a vacuum pump, to evacuate gas from around the water adsorbent. Adsorption will typically be carried out at near atmospheric pressure. In other embodiments, temperature swing adsorption is performed to achieve water collection. This can be achieved using direct heating methods, or in some cases using magnetic induction swing adsorption.

Magnetic swing water adsorption equipment

In some cases, the device may be configured as a magnetic pendulum water adsorption device to collect moisture from a water-containing gas, such as the atmosphere. One form of this type of device 200 is illustrated in FIG. 1A or FIG. 1B.

Fig. 1A and 1B illustrate an apparatus 200 for capturing moisture from an aqueous gas, the apparatus 200 using a shaped water adsorption complex formulated with magnetic particles as discussed above. The device 200 comprises a cylindrical housing 205, the cylindrical housing 205 comprising an inlet 208 and an outlet 211. The shell 205 contains a packed bed 215 of the shaped water-adsorbing composite 100 (see fig. 2C), the composition of the shaped water-adsorbing composite 100 being described in more detail below. Fluid distribution discs 210 near the bottom (base) and lid/top of the housing 205 serve to retain the shaped adsorbent material 215 between the discs 205. Each fluid distribution tray 210 comprises a metal tray that is drilled with a plurality of holes to allow fluid to flow through the filled shaped adsorbent material. The shaped adsorbent material forms a compressed packed bed between the disks 210 and is compressed therebetween such that the adsorbent shaped body 100 is tightly packed therein, thereby avoiding any short flow loops.

In the embodiment shown in fig. 1A, Alternating Current (AC) induction coil 250 is located within packed bed 215 of formed water adsorption composite 100 (fig. 2C) and is surrounded by packed bed 215. The induction coil 250 is configured to apply an AC magnetic field to the packed bed 215 of formed water adsorption composite. The induction coil 250 is embedded within the packed bed 215 to optimize the use of the applied magnetic field when the induction coil 250 is operated.

The housing 205 includes a magnetic damping material 255 to reduce magnetic field leakage (magnitical field leakage) from the container to the surrounding environment. This may be important in some applications where the magnetic field may severely affect the operation of nearby equipment or irradiate a person or object.

In the embodiment shown in fig. 1B, an Alternating Current (AC) induction coil 250 is located outside of, but at a position around, the shell 205, which extends around the packed bed 215 of the formed water adsorbent composite 100. Likewise, induction coil 250 is configured to apply an AC magnetic field to the packed bed 215 of formed water adsorption composite. However, it should be appreciated that the positioning of the induction coil 250 is not as energy efficient as shown in fig. 1A due to losses through the material of the housing. Further, although not shown in fig. 1B, an additional housing may be used to enclose the induction coil, the additional housing including magnetic damping material 255 to reduce leakage of the magnetic field to the surrounding environment.

In use, an aqueous gas is flowed through the packed bed of shaped bodies 215 such that the shaped water-adsorbing composite adsorbs water from the aqueous gas. Once the packed bed 215 reaches the desired saturation level (typically 70% to 90% saturation point), the induction coil 250 is operated to apply an alternating magnetic field to generate heat within the shaped water-adsorbing composite to release at least a portion of the adsorbed water therefrom into the product fluid stream. Thus, the formed water adsorbent composite undergoes magnetically induced vacuum swing adsorption to capture water from the aqueous gas fed into the packed bed 215 of the formed water adsorbent composite.

Although not shown in fig. 1A or 1B, a condenser may be used to subsequently separate the moisture of the product fluid stream (typically a gas with entrained water vapor) to produce a captured water product. Low or reduced pressure (sometimes referred to as a vacuum environment), or a positive pressure gas stream, e.g., a stream of an aqueous gas or another gas such as an inert gas or other dry gas, directs the released water to the condenser.

The above-described method is applied cyclically, in which the steps of adsorbing water in the formed water adsorption complex 100, releasing the adsorbed water by applying an AC magnetic field, and condensing the water are performed in repeated cycles, thereby continuously producing water.

Temperature-changing water adsorption equipment

A temperature swing water collection apparatus 300 configured in accordance with an embodiment of the present invention is illustrated in fig. 1C, 1D, and 1E.

The apparatus 300 shown in fig. 1C and 1D is configured to use the waste heat of the peltier device 310 to heat a shaped MOF complex 100 (the composition of which is described in more detail below) placed in thermal contact (via a heat sink 320, discussed below) with a hot side 312 of the peltier device 310 to facilitate desorption of adsorbed water in the shaped MOF complex. The cold side 314 of the peltier device 310 may simultaneously be used to condense the desorbed water vapor, and this condensed water may be collected as a liquid product below the peltier device 310.

Peltier device

A peltier device is a thermoelectric device having the ability to convert electrical energy into a temperature gradient, which is commonly referred to as the "peltier effect". An electrical current applied to a pair of dissimilar metallic materials results in a hot surface on one side of the semiconductor and a cold surface on the other side of the semiconductor and produces a heat flow through the semiconductor perpendicular to the current flow. When current is applied from an n-type semiconductor to a p-type semiconductor, a single pair of p-type semiconductor material and n-type semiconductor material coupled in series is sufficient to create a temperature gradient. The cold side of the peltier element is formed where electrons flow from the p-type semiconductor to the n-type semiconductor with a heat flow Q_disOccurs at the transition from an n-type semiconductor to a p-type semiconductor. It will be appreciated that the dissipated heat (dis-plated heat) of the peltier device is higher than the electrical power due to the absorbed heat on the cold side of the peltier device.

Peltier devices are typically made up of 3 to 127 semiconductor pairs per device. The semiconductors are electrically connected in series and thermally connected in parallel. The heat flow in a commonly used peltier device is between 1W and 125W. The temperature difference between the hot and cold sides of a peltier device is up to 70K for a single stage device and up to 130K for a multi-stage device (several peltier elements connected in series).

Due to the high temperature difference and thus the material expansion difference between the cold side and the hot side, mechanical stresses can occur in the peltier device. Therefore, the size of peltier devices is typically limited to 50mm x 50mm to keep such mechanical stress issues low. Current peltier devices are also subject to inefficiencies of about 10% of possible carnot efficiency, primarily due to the available nature of the semiconductor materials used in the particular peltier device.

Temperature-changing desorption

Fig. 1C and 1D illustrate an embodiment of a temperature swing water collection apparatus 300. As shown, the device 300 includes a sealable container 330 having a container body 332 and a sealing cover 334. The container body 332 houses a polycarbonate panel 338, the polycarbonate panel 338 being positioned with a spacer 339 and spaced from the bottom of the container body 332 to define within the container 330 (i) an upper water adsorption-desorption chamber 340; and (ii) a lower condenser chamber 342. The container 330 may be sealed using a removable seal cap 334. A water collecting device 350 is installed in the container main body 332. The water collection device 350 comprises the following sections:

(A) a heat sink 320, the heat sink 320 comprising a plurality of spaced apart fins 352. Although not shown in detail, the spaces between each of the spaced apart fins 352 are filled with a formed water adsorbent composite 100 in which a packed bed 355 is formed in the formed water adsorbent composite 100;

(B) a peltier device 310 having a hot side 312 in thermal communication with a heat sink 320 and a cold side 314 in thermal communication with the gas space of a lower condenser chamber 342. The peltier device 310 is configured to heat the shaped water-adsorbing composite 100 in the heat sink 320 (see below) during the desorption phase of the water collection cycle; and

(C) a condenser system 360, the condenser system 360 located in the condenser chamber 342, which uses the cold side 314 of the peltier device 310 to cool a fluid stream of water vapor produced from the packed bed 355 to condense and collect water as a liquid product at the bottom of the container 330.

The apparatus 300 shown in fig. 1C, 1D and 1E utilizes both the cold side 314 and the hot side 312 of the peltier device 310 during the desorption phase of the temperature swing water collection cycle. The dissipated heat of the hot side 312 of the peltier device 310 can be used for a temperature swing desorption cycle to heat the shaped MOF complex 100 during the desorption phase to desorb water from the shaped MOF complex 100. The cold side 314 may be used to absorb heat from the water vapor produced and condense the water in a condenser system/chamber so that the water can be collected as a liquid product.

For this application, it will be appreciated that the key criteria in selecting a peltier device are:

the ability to provide sufficient heating so that water desorbs from the MOF composite at the hot side of the peltier device.

The ability to provide sufficient cooling to the cold side of the peltier device so as to be below the dew point where condensation occurs in the condenser system.

Other factors, including reliability and corrosion resistance.

The lowest power peltier device capable of doing this will result in the most efficient device.

In the illustrated system (see fig. 1D), the water collection device 350 is mounted within a 10L sealable food container. The heat sink 320 includes two NH-D15S (raw Computer distribution ges.m.b.h., vienna (austria)) CPU coolers. However, it should be understood that other suitable heat sink configurations may be equivalently used. This type of CPU cooler has 1.0634m²Due to thermal stress issues (as previously discussed), this type of heat spreader 320 is used when the size of the peltier device is limited to a size of about 40mm × 40mm, due to the free volume of 0.9967L the heat spreader 320 ensures that heat is distributed from the peltier device 310 to a much larger surface that can be used to conduct heat transfer to heat the shaped MOF complex in the packed bed 355.

The heat sink 320 has a mounting socket that is perfectly mounted to the peltier device and conducts heat to the 90 metal fins 352 using 12 heat pipes 356. 45 fins 352 are stacked on top of each other at a distance of 1.92 mm. Two of these stacks of heat sinks 320 are assembled side-by-side onto the mounting sockets of heat sinks 320.A 12V fan 370 is installed between the two stacks of heat sinks 320 to provide a flow of air through the free volume between the fins 352 during the adsorption and desorption phases. However, it should be understood that the fan may be included in other locations stacked adjacent to the heat sink 320. The heat sink 320 and the peltier device 310 are mounted to a polycarbonate plate 338. The heat sink 320 is fixed to the peltier device 310 using screws. Thermal grease (heat grease) is applied to the connection surface between the peltier device 310 and the heat sink 320 to ensure sufficient heat flow through the connection. The fan 370 is selected to generate from 3m³H to 200m³Flow rate per hour. In the illustrated embodiment, the fan comprises a fan capable of up to 140m³12V fan with flow rate/h. In most test runs, the fan was set to produce about 30m³Low setting of/h. The flow rate may be adjusted according to ambient humidity conditions.

Although not illustrated, an additional small heat sink may be secured to the cold side 314 of the peltier device 310 to increase the surface area for water condensation. It should be understood that the cold side 314 of the peltier device 310 with a small heat sink forms the condenser system 360 of the water collection device 350.

As indicated above, the free volume between fins 352 is filled with the shaped MOF complex 100. In the illustrated embodiment (fig. 1C-1E), MOF composite 100 comprises triangular pellets of aluminum fumarate (see fig. 1) having an edge length S of 1.5mm and a length L of 3 mm. The heat sink 320 is sealed with a mesh (not shown) having pores small enough to hold the pellets between the fins 352 of the heat sink 320. The mesh comprises a commercially available slatted cover mesh (fly wire) with 1mm holes. 200.30g of MOF pellets were packed between fins 352. This corresponds to a packing density of 0.20 kg/L. Therefore, 198.30g of aluminum fumarate was used as adsorbent in the water collecting device 350.

In the illustrated test setup (see fig. 1D and 26), 6 thermocouples 375 were fixed into the heat sink 320 in order to observe the temperature and temperature distribution in the MOF packed bed 355 during the desorption phase. All 6 thermocouples were placed in one of the two sides of the heat sink 320. 3 of the thermocouples are at the center of the fin 352 at 3 different heights. The other 3 thermocouples were at 3 different heights to the right of the fin 352.

The catchment circulation (WHC) using the apparatus 600 may be designed to have two phases:

1. an adsorption phase (fig. 1e (a)) -during this adsorption phase, the sealable container 330 is opened to the environment (i.e. the lid 334 is removed) and air is blown through the MOF packed bed 355 in the heat sink 320 using a fan 370. Water in the air is adsorbed by the formed water adsorption complex 100 of the packed bed 355. During this phase, the peltier device 310 is turned off. Once the packed bed 355 reaches the desired saturation level (typically 70% to 90% saturation point), the cover 334 is placed over the vessel body 332 to seal the vessel 330, and the peltier device 310 is opened to begin the desorption phase.

2. A desorption phase (fig. 1e (b)) -wherein the peltier device 310 is turned on and the packed bed 355 in the heat sink 320 is heated to an elevated temperature to release at least a portion of the adsorbed water from the formed water adsorption complex 100 in the packed bed 355 into the product fluid stream while the vessel 330 is sealed closed. The relative humidity in the container 330 increases to a high value and water condenses on the cold side 314 of the peltier device 310. After each catchment cycle, liquid water is collected under the cold side 314 of the peltier device 310.

The water collection cycle described above is cyclically applied, in which the steps of adsorbing water in the formed water adsorption complex 100, releasing the adsorbed water by operating the peltier device, and condensing the water are performed in repeated cycles, thereby continuously producing water.

Adsorption media

The apparatuses illustrated in fig. 1A-1E each use a shaped water adsorption complex 100 (fig. 2C) in a packed bed as a water adsorbent. However, it is to be understood that the metal organic framework composite material may be provided in the device of the present invention in any form suitable for the particular device configuration. The inventors contemplate that this may be in a variety of composite forms including, but not limited to, shaped bodies (e.g., pellets or extrudates), coatings, plates, sheets, ribbons, or the like.

Shaped metal-organic framework composites

The shaped water-adsorbing composite 100 (fig. 2C) used in the apparatus discussed with respect to the apparatus shown in fig. 1A-1E comprises a mixture of a water-adsorbing Metal Organic Framework (MOF) and a hydrophilic binder optimized for use in a packed bed adsorption system. The mixture comprises at least 50 wt% of a water-adsorbing metal-organic framework and at least 0.1 wt% of a hydrophilic binder.

In the embodiment shown in fig. 1A and 1B, the formed water adsorbent composite 100 is configured to collect water using a magnetic induction swing adsorption system. In these embodiments, the formed water-adsorbing composite additionally comprises from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm. The use of magnetic particles in the form of a composition enables the induced heat to be used for desorption of water. This type of composite material, which is referred to as a magnetic backbone composite, combines the exceptional adsorption properties of MOFs with the high efficiency of magnetic induction heating.

The metal-organic framework composite material may be formed into any suitable configuration for filling an adsorption system. In the present invention, the metal-organic framework composite is exemplified as a water-adsorbing composite 100 having an elongated shape with a triangular cross section, for example, as shown in fig. 2C. However, it is understood that other shapes, such as spherical, cylindrical, cubic, ovoid, or the like, may be equivalently used.

Referring to fig. 2C, the formed water-adsorbing composite 100 comprises an elongated body having an equilateral triangular cross-sectional shape. The sides S of the equilateral triangle are at least 1mm in length, preferably between 1.0mm and 1.5mm in length. The length (longitudinal length, L) of the formed water-adsorbing composite is preferably from 1mm to 5mm, more preferably from 1mm to 4 mm. The elongated triangular shape is selected to increase the packing density of the formed water adsorbent composite 100 within a packed bed (e.g., packed bed 215 shown in fig. 1A and 1B). Previous studies have shown that this shape has one of the highest packing densities in a packed bed configuration. For optimal utilization and heat generation from the applied heat source, high packing densities are preferred. For example, a cylindrical pellet shape has a packing density of about 0.19 kg/L. The elongated equilateral triangular pellets had a packing density of about 0.29 kg/L.

Water-adsorbing metal-organic framework

The water-adsorbing metal-organic framework used in the formed water-adsorbing composite 100 may be selected from a range of suitable water-adsorbing MOFs. A variety of Water-adsorbing MOFs are known, for example as discussed in Furukawa et al, "Water addition in porous metals-Organic Frameworks and Related Materials" Journal of the American chemical Society 136(11), 3 months 2014 and H W B Teo and A Chakraborty 2017IOPCon, Ser. mater. Sci.Eng.272012019, the contents of these references should be understood as being incorporated by these references into this specification. In selected embodiments, the water-adsorbing metal-organic framework comprises at least one of: aluminum fumarate, MOF-303(Al), MOF-573(Al), MOF-801 (Zr)₆O₄(OH)₄(fumarate salt)₆)、MOF-841(Zr₆O₄(OH)₄₍MTB)₂(HCOO)₄(H₂O)₄)、M₂Cl₂BTDD (including Co)₂Cl₂BTDD), Cr-soc-MOF-1, MIL-101(Cr), CAU-10, alkali metal (Li +, Na +) doped MIL-101(Cr), MOF-802 (Zr)₆O₄(OH)₄(PZDC)₅(HCOO)₂(H₂O)₂)、MOF-805(Zr₆O₄(OH)₄[NDC-(OH)₂]₆)、MOF-806(Zr₆O₄(OH)₄[NDC-(OH)₂]₆)、MOF-808(Zr₆O₄(OH)₄(BTC)₂(HCOO)₆)、MOF-812(Zr₆O₄(OH)₄(MTB)₃(H₂O)₄) Or mixtures thereof. Preferred water-adsorbing metal-organic frameworks are aluminum fumarate, MOF-303(Al), MOF-801, MOF-841, M₂Cl₂BTDD, Cr-soc-MOF-1 and MIL-101 (Cr).

The selection of optimized water-adsorbing MOFs involves a number of considerations, including:

1. water stability-MOF should be water stable.

2. Reproducibility of adsorption, the MOF should retain the adsorption capacity after a number of adsorption/desorption cycles, preferably at least 10 cycles, more preferably at least 100 cycles.

3. The MOFs should be easy to produce from readily available precursor materials.

4. High water absorption from the air, even at low humidity values.

5. Good affinity for water. The MOFs should have a good enough affinity for water to enable them to adsorb water, but not so high an affinity for water that excessive energy is required to desorb water therefrom. Here, the thermodynamics of the adsorption and desorption of water need to be taken into account to ensure that the MOF does not require excessive energy (kJ/mol MOF) to desorb water therefrom and thereby adversely affect the energy efficiency of the system. For water adsorbed on MOFs, the typical heat of adsorption of water by MOFs is in the range from 10kJ/mol MOF to 100kJ/mol MOF (550kJ/kg to 5500 kJ/kg). Careful MOF selection is important to the operation of the device, as the cost of water will be directly related to the energy required to desorb the water from the MOF.

In the case where MOFs are required for water production for human consumption, MOFs and other materials must also comply with the regulations of relevant countries for food products for human consumption. Applicants have found that in these embodiments, the water-adsorbing MOFs preferably comprise aluminum fumarate (AlFu) MOFs. The water adsorption properties of AlFu are disclosed in a number of studies available in the open literature.

Aluminum fumarate

Aluminum fumarate (AlFu) is used as the preferred MOF in the formed water adsorbing complex 100. The structure and water adsorption properties of AlFu are well known, for example as described in detail in Teo et al (2017), Experimental study of the exotherms and kinetics for the adsorption of water on aluminum Fumarate.International journal of Heat and Mass Transfer, Vol.114, 11 months 2017, p.621-627, the contents of which are to be understood as being incorporated by reference into the present specification. As outlined by Teo, the crystal structure of AlFu is similar to MIL-53 in that it also consists of an infinite number of Al OH Al chains connected by fumarate linkages.AlFu has the formula [ Al (OH) (O) with square channels₂C-CH＝CH-CO₂)]Permanent porous 3D structure.

In general, aluminum fumarate was chosen as the preferred MOF choice for the water capture device and system of the present invention because:

1. ease of manufacture-such MOFs can be synthesized in water. After synthesis, processing of MOFs is straightforward, as outlined in the examples.

2. Good thermal stability, and is highly water stable (unlike many other MOFs);

3. it is robust to operation under ambient conditions (robust) and can withstand multiple temperature cycles without degradation.

4. It has well-studied water adsorption behavior;

5. high water absorption from air, even at low humidity values; depending on the relative humidity, aluminum fumarate has a water capacity between 0.09 grams of water per gram of MOF to 0.5 grams of water per gram of MOF. The typical heat of adsorption of aluminum fumarate on water is well known and ranges between 60kJ/mol and 30kJ/mol depending on the ambient humidity.

6. It can be produced inexpensively and easily using non-toxic ingredients/precursor materials-i.e., an environmentally friendly synthetic method, and is easy to operate and process; and

7. the cost of the components is low.

However, it is to be understood that the MOF component of the invention is not limited to aluminum fumarate, and that other water adsorbing MOFs may also be used in the composition of the water adsorbing complex.

Hydrophilic adhesive

The selection of a suitable binder is also important to the bulk properties of the formed adsorbent. The inventors have surprisingly found that a hydrophilic binder must be used to impart optimal water-adsorbing properties to the formed water-adsorbing composite. The inventors have also found that non-hydrophilic binders, and in particular hydrophobic binders (e.g. cellulose siloxane), reduce/reduce the water-adsorbing properties of the formed water-adsorbing composite. Thus, the use of a hydrophilic binder is important for optimal moisture capture properties of the packed bed water adsorption system. However, although other binders are also possible, it should again be noted that particularly suitable hydrophilic binders may be selected from at least one of the following: hydrophilic cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl methylcellulose (HPMC), ethyl hydroxyethyl cellulose, methylcellulose or carboxymethylcellulose (CMC); or polyvinyl alcohol (PVA), as previously set forth in this specification. As indicated in the examples below, one exemplary hydrophilic binder is hydroxypropyl cellulose (HPC).

Lubricant agent

The formed water-adsorbing composite may also contain a lubricant content, preferably less than 0.5 wt.% lubricant, and more preferably less than 0.1 wt.% lubricant. Suitable lubricants include surfactants and salts thereof. Examples of suitable lubricants include magnesium stearate, alumina, sodium oleate, glycerides, diglycerides, triglycerides, fatty acids, oils (including silicone oils and mineral oils), and mixtures thereof. As previously mentioned, the lubricant content may aid in the forming and forming process of the formed water-adsorbing composite.

Magnetic particles

The formed water adsorbent composite may be configured to collect water using a magnetic induction swing adsorption system. In these embodiments, the formed water-adsorbing composite 100 (fig. 1) comprises a mixture comprising at least 50 wt% of a water-adsorbing metal-organic framework, at least 0.1 wt% of a hydrophilic binder, and from 0.2 wt% to 10 wt% of magnetic particles having an average particle diameter of less than 200 nm. The mixture is optimized for use in a packed bed adsorption system.

As previously discussed, a variety of magnetic particles may be used in the shaped adsorbent bodies of the present invention. In embodiments, the magnetic particles comprise ferromagnetic, paramagnetic or superparamagnetic particles (typically microparticles or nanoparticles). In an embodiment, the magnetic particles comprise a metal chalcogenide. Suitable metal chalcogenides include magnetic particles comprising an element or elemental form with at least one of O, S, Se or TeAny combination of elements of M or ionic forms thereof in combination, said M being selected from at least one of: li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi or combinations thereof. In some embodiments, the crystallization promoter comprises a compound having the formula M_xN_yC_zWherein M, N is selected from at least one of the following: li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, C being selected from at least one of O, S, Se, Te, x being any number from 0 to 10, Y being any number from 0 to 10, and z being any number from 0 to 10. In some embodiments, the metal chalcogenide particles may have a core-shell structure, wherein the core comprises at least one metal chalcogenide as previously described and the shell comprises at least one metal chalcogenide as previously described. In some forms, the core-shell structure may include a plurality of shells. In embodiments, the magnetic particles comprise at least one of: MgFe₂O₄、Fe₃O₄C-coated Co, CoFe₂O₄、NiFe₂O₄Pyridine-2, 6-diamine functionalized SiO₂Or pyridine-2, 6-diamine functionalized Fe₃O₄。

The advantages of these magnetic materials are:

local heat generation-i.e. heat can be generated in situ in the material by applying an AC magnetic field (as discussed previously) rather than using an external heat source;

rapid heating of the material, due to local heat generation, avoiding heat losses and energy losses by thermal heating of the surrounding material; and

high energy conversion efficiency

The combination of magnetic particles and MOFs forming a magnetic framework composite material results in an adsorbent that has exceptional adsorption behavior due to the MOFs and high efficiency of induction heating due to the magnetic particles.

Examples

The following examples use AlFu as water in a magnetic backbone composite to adsorb MOF. It is to be understood that magnetic framework composite materials can adsorb MOFs using a variety of other waters by directly replacing the MOF within a pellet of magnetic framework composite material.