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WO2002072242A1 - Dispositif d'echange de chaleur et d'humidite - Google Patents

Dispositif d'echange de chaleur et d'humidite Download PDF

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Publication number
WO2002072242A1
WO2002072242A1 PCT/US2002/007709 US0207709W WO02072242A1 WO 2002072242 A1 WO2002072242 A1 WO 2002072242A1 US 0207709 W US0207709 W US 0207709W WO 02072242 A1 WO02072242 A1 WO 02072242A1
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WO
WIPO (PCT)
Prior art keywords
cell according
chamber
fluid
flow
composite membrane
Prior art date
Application number
PCT/US2002/007709
Other languages
English (en)
Inventor
Joseph M. Serpico
Scott Ehrenberg
Original Assignee
Dais-Analytic Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dais-Analytic Corporation filed Critical Dais-Analytic Corporation
Priority to JP2002571197A priority Critical patent/JP2004535270A/ja
Priority to GB0321274A priority patent/GB2389063A/en
Priority to CA002440961A priority patent/CA2440961A1/fr
Publication of WO2002072242A1 publication Critical patent/WO2002072242A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/268—Drying gases or vapours by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • F24F3/147—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification with both heat and humidity transfer between supplied and exhausted air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D21/0015—Heat and mass exchangers, e.g. with permeable walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
    • F28F21/065—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material the heat-exchange apparatus employing plate-like or laminated conduits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • F24F2003/1435—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification comprising semi-permeable membrane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to devices and apparatus for transfer of heat and water between fluids, via a composite polymer membrane.
  • a unitary humidity exchange cell (or HUX), as the name implies, is an element of a device that is capable of transferring water or other highly polar liquid or gas from one side of the cell to the other by action of a difference in some quantity or gradient across said cell.
  • a key operational characteristic of the HUX cell is that a difference of some intensive or extensive property of the system (relative to the surrounding) leads to a gradient change of said property to effect mass transfer of water or some other highly polar liquid or gas from one side of the membrane to the other with or without an accompanying flow of electrons, protons, ions or molecules other than said water or other highly polar liquid or gas.
  • a finite gradient across the membrane must exist in some quantity; examples are vapor pressure, osmotic or hydrostatic pressure, chemical, thermochemical, electrochemical, magnetochemical potential, as well as thermal (temperature or heat content), electric, electromagnetic, thermoelectric, or electrothermal potential difference.
  • the system attempts to reach a thermodynamic equilibrium by transporting water or some other highly polar liquid or gas from one stream to the other.
  • the orientation of the streams to one another is considered arbitrary for the invention; these may be counter flow, coflow, crossflow, mixed flow or any other geometric arrangement of one or more streams.
  • Water or some other highly polar liquid or gas transport occurs until the imposed gradient can no longer meet the physicochemical constraints of the system required to sustain the motion.
  • the exchange of water or some other highly polar liquid or gas between the streams is slow, but this may be due to some other limiting factor, such as, boundary layer effects, concentration polarization, hydrostatic pressure lag or gravity, surface tension effects, and convective or frictional effects.
  • the exchange or transport of water or some other highly polar liquid or gas is rate-limiting if the permeability of the membrane to water or some other highly polar liquid or gas is poor.
  • an important object of the invention is that hydrophilic polymer membrane has high permeability to water or some other highly polar liquid or gas; more than necessary for most applications.
  • the hydrophilic polymer membrane (or formulation) must be mechanically supported and there must be means to supply the two streams to said surfaces.
  • a second object of the invention is that the three sub-elements be fabricated as one unit by conventional means at low cost. This requires that the hydrophilic polymer wet the support, achieve intimate contact and demonstrate exceptional adhesion to it. Therefore, a third object of the invention is that the support be a polyolefin or blend thereof such that one component of said hydrophilic polymer is similar in chemical structure to one component of the support.
  • HUX cell design is general in that water (liquid or vapor) or other highly polar material (liquid or vapor) can be transferred between any two fluids.
  • applications are per-vaporation humidification and dehumidification of fuel cell streams in stacks and devices, drying gases at pressure, tertiary oil recovery, process control for chemical manufacture of chemicals for which water is a reactant, isolation of minerals from mining fluids, industrial separation of oil-water emulsions, microfiltration and ultrafiltration of colloidal suspensions and biological or organic macromolecules for purification, maintaining water content of methanol in direct methanol fuel cells, reverse osmosis for isolation of fresh water from brine, electrolysis cells, dialysis, electro-dialysis, piezo-dialysis, electro-osmosis and chloro-alkali cells.
  • the present invention relates to cells for transferring heat and moisture between a first fluid and a second fluid.
  • a cell comprises at least one composite membrane, disposed between at least one first chamber for flow of the first fluid therethrough and at least one second chamber for flow of the second fluid therethrough; whereby heat and moisture is transferable between the first fluid and second fluid via the composite membrane.
  • the composite membrane may comprise an at least partially sulfonated humidity-conducting polymer comprising residues derived from at least one arylvinyl monomer; and a reinforcing substrate bonded thereto.
  • the cell may additionally include at least one spacer disposed on a surface of the composite membrane.
  • the spacer(s) may have a dimension normal to the surface of the composite membrane corresponding to a height of the first chamber; the longitudinal axis of the at least one, spacer may be oriented parallel to a direction of flow of the first fluid in the first chamber.
  • the direction of flow of the first fluid in the first chamber may be orthogonal to a direction of flow of the second fluid in the second chamber, or it may be opposite to it.
  • a plurality of synthetic polymer ribs are used as spacers; in others, the spacer is merely a bead of an adhesive composition; in still others, the spacer is a corrugated sheet composed of paper or plastic.
  • the invention also relates to cell containing a plurality of composite membranes, and a plurality of alternating first chambers and second chambers, each separated by a composite membrane.
  • the reinforcing substrate of the composite membrane may be a nonwoven fabric, composed of synthetic fibers, particularly one or more polyolefins.
  • the humidity-conducting polymer of the composite membrane may include an additive selected from the group of antioxidants, biocides, flame retardants, uv stabilizers, hydrophilic plasticizers, and mixtures thereof, particularly, antioxidant(s), biocide(s), and flame retardant(s).
  • the humidity-conducting polymer may be crosslinked using a peroxide initiator and an organometallic enolate coupling agent, particularly, 1 ,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane and aluminum acetoacetonate, or 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and aluminum acetoacetonate.
  • organometallic enolate coupling agent particularly, 1 ,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane and aluminum acetoacetonate, or 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and aluminum acetoacetonate.
  • FIG. 1 shows a composite membrane for use in a humidity exchange cell according to present invention.
  • FIG. 2 is a partially exploded view of a humidity exchange cell according to the present invention.
  • FIG. 3 is a graph showing high heat and water transfer using a humidity exchange cell according to the present invention.
  • FIG. 1 shows a single composite membrane 10 for use in a humidity exchange cell according to the present invention.
  • the membrane includes a continuous film of a humidity-conducting polymer 12 bonded to a reinforcing substrate 14 in the form of a cross-laid mesh or netting. Reinforcing substrate 14 strengthens the membrane so it can be handled, and allows the membrane to withstand pressure differentials without deflecting.
  • the other side of the membrane is a smooth surface of humidity-conducting polymer 12.
  • the height of spacer 16 sets the layer-to-layer spacing. Air channels in the humidity exchange cell are formed by spacers 16 when they rest against the smooth surface of the membrane that is placed on top of it.
  • the humidity-conducting polymer may be an at least partially sulfonated copolymer comprising residues derived from at least one arylvinyl monomer. Accordingly, the polymer includes repeating units of formula III, derived from an arylvinyl monomer, in addition to one or both of the repeating units of formulas I and II, derived from olefin monomers.
  • R ⁇ , R ⁇ , R3, R4 are chosen independently from the group consisting of hydrogen, nitrile, phenyl and lower alkyl; R ⁇ is hydrogen, chlorine or lower alkyl; R ⁇ is hydrogen or methyl; R 7 is -COOH, -SO3H, -P(0)(0R8)0H, -R9-COOH, -R9-SO3H, -R 9 -
  • R 8 is hydrogen or lower alkyl
  • R 9 is lower alkylene
  • Ar is phenyl
  • m, n, p, and q are zero or integers from 50 to 10,000.
  • the humidity-conducting polymer may be a block, graft or statistical copolymer derived from arylvinyl monomers.
  • arylvinyl monomers Some suitable polymers are described in US Patent Nos. 5,468,574; 5,679,482; and 6,110,616; the disclosure of each of these is incorporated by reference herein in its entirety.
  • Block and graft copolymers contain relatively long segments made up of a homopolymer derived from one of the comonomers.
  • the term "statistical" is used herein to refer to polymers that do not contain long segments made up of homopolymer, and to distinguish these from block and graft copolymers.
  • the statistical polymers do not contain more than 15 percent of the total amount of arylvinyl monomer in blocks of arylvinyl monomer of more than 3 units. More preferably, the statistical polymers are not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon-13 NMR spectrum of the statistical polymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons. .
  • a statistical copolymer is a well-defined term of art (see G. Odian, Principles of Polymerization, 1991), and the use of the term herein is consistent with the commonly understood usage.
  • Statistical copolymers are derived from the simultaneous polymerization of two monomers and have a distribution of the two monomer units along the copolymer chain that follows Bernoullian (zero-order Markov), or first or second order Markov statistics.
  • the polymerization may be initiated by free radical, anionic, cationic or coordinatively unsaturated (e.g., Ziegler-Natta catalysts) species. According to Ring et al., (Pure Appl.
  • a free radical copolymerization for the active end, in the case of one embodiment, a styryl or butadienyl radical, to have essentially no selectivity for styrene vs. butadiene. If so, the statistics will be Bernoullian, and the copolymer obtained will be random. More often than not, there will be a tendency for the propagating chain end to have some selectivity for one monomer or the other. In rare cases block copolymers can be derived from the simultaneous copolymerization of two monomers when the preference of the propagating chain ends for adding the opposite monomers is very low. The resulting polymer would be categorized as a block copolymer for the purposes of the present invention.
  • Statistical copolymers generally display a single glass transition temperature.
  • Block and graft copolymers typically display multiple glass transitions, due to the presence of multiple phases.
  • Statistical copolymers are, therefore, distinguishable from block and graft copolymers on this basis.
  • the single glass transition temperature reflects homogeneity at the molecular level.
  • An additional consequence of this homogeneity is that statistical copolymers, such as those of styrene and butadiene, when viewed by electron microscopy, display a single phase morphology with no microphase separation.
  • block and graft copolymers of styrene/butadiene are characterized by two glass transition temperatures and separation into styrene-rich domains and butadiene-rich domains.
  • membranes of the invention which are produced from statistical copolymers originally having a single glass transition temperature and a single phase morphology do not necessarily exhibit a single phase morphology or a single glass transition temperature after sulfonation because of chemical changes in the polymer effected by the sulfonation, in combination with the physical changes effected by the casting processes of the invention.
  • the humidity-conducting polymers for use in the humidity exchange cells of the present invention are derived from the polymerization of arylvinyl monomers and which, therefore, contain pendant aryl or aromatic moieties.
  • Arylvinyl monomers are defined herein as monomers that contain a vinyl group substituted with an aryl, haloaryl or alkyl- substituted aryl group.
  • An example of a monomer containing a vinyl group substituted with an aryl is styrene, an example of a monomer containing a vinyl group substituted with a haloaryl group is chlorostyrene, and examples of monomers containing a vinyl group substituted with an alkyl-substituted aryl group are p-octylstyrene and vinyl toluene.
  • One or more arylvinyl monomers may be copolymerized with olefin comonomers to produce a polymer which may be sulfonated; the resulting sulfonated copolymers may be used to form the membranes of the present invention.
  • Suitable arylvinyl monomers that can be employed to prepare the polymers for sulfonation include, for example, styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene and all isomers of these compounds.
  • Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene; ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para- methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof, and the like.
  • a more preferred arylvinyl monomer is styrene.
  • Residues derived from vinyl toluene and chlorostyrene may be less readily sulfonated than those from styrene; therefore, it may be desirable to include utilize vinyl toluene and chlorostyrene along with arylvinyl monomers that result in residues that may be more readily sulfonated, such as styrene or ⁇ -methyl styrene, rather than as the sole arylvinyl component of the polymer.
  • the aryl or aromatic moieties may be sulfonated at one or more positions on the aromatic rings to yield polymer chains having pendant aryl sulfonate groups.
  • Humidity-conducting polymers may also include residues derived from at least one olefin monomer, in addition to those derived from at least one arylvinyl monomer.
  • Preferred olefin monomers include monoolefins, such as ⁇ -olefins and strained ring olefins, and diolefin monomers such as butadiene and isoprene.
  • ⁇ -Olefins include ethylene and C ⁇ o olefins having ethylenic unsaturation in the ⁇ - or 1- position, such as ethylene, propylene, butylene, and isobutylene.
  • Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 3 to about 20, preferably from 3 to about 12, more preferably from 3 to about 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1 , 4-methyl-1-pentene, 1-hexene or 1-octene or ethylene in combination with one or more of propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene.
  • Preferred monoolefin monomers are ethylene, propylene, 1- butene, 2-butene, 1- pentene, 4-methyl-l-pentene, 1-hexene, arid 1-octene.
  • Preferred strained ring olefins are the various isomeric vinyl-ring substituted derivatives of cyclohexene and substituted cyclohexenes, norbornene and C ⁇ alkyl or Ce. 10 aryl substituted norbomenes, including 5-ethylidene-2-norbornene.
  • ⁇ -olefins including, for example, ⁇ -olefins containing from 3 to about 20 carbon atoms such as propylene, butene-1, 4-methyl-1 -pentene, hexene-1 or octene-1 are not examples of strained ring olefins.
  • Preferred statistical arylvinyl polymers are ethylene/styrene, ethylene/propylene/styrene, ethylene/styrene/ norbornene, and ethylene/propylene/styrene /norbornene copolymers.
  • the polymer may also contain residues derived from other comonomers, for example, acrylate monomers.
  • copolymers derived from diolefins, for example, butadiene and isoprene copolymers may contain residual unsaturation. These are typically hydrogenated, or reduced, prior to being sulfonated.
  • the sulfonated copolymers may be blended with other sulfonated copolymers or with conventional polymers in order to form composite membranes for use in the present invention.
  • a humidity-conducting polymer for use in a humidity exchange cell of the present invention typically contains at least 20 weight % of residues derived from styrene. More preferably, the copolymer contains from 20 to 50 weight % styrene, and most preferably, about 45 weight % styrene. .
  • the range of weight average molecular weight (M w ) of the polymer of the invention is from about 20,000 grams/mole to about 1,000,000 grams/mole, and preferably from about 50,000 grams/mole to 900,000 grams/mole.
  • the sulfonated polymer used for the membranes of the present invention are preferably water-insoluble.
  • Water-insoluble is defined as having a solubility of less than 0.5 grams of polymer in 100 grams of water at 100°C.
  • Suitable humidity-conducting polymers include sulfonated, block styrene-ethylene-butylene-styrene copolymers, sulfonated, reduced, statistical styrene-butadiene copolymers and sulfonated statistical styrene- ethylene copolymers.
  • Statistical styrene-butadiene copolymers may be obtained from Goodyear; block styrene-ethylene-butylene-styrene copolymers may be obtained from Shell and statistical ethylene-styrene copolymers (ethylene styrene interpolymers (ESI)) may be obtained from Dow Chemical.
  • the Dow ESI polymers include the pseudorandom interpolymers as described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are incorporated herein by reference in their entirety.
  • the unsaturated residues in the copolymer membranes of the invention are may selectively hydrogenated prior to sulfonation of aromatic groups derived from the styrene residues.
  • the amount of unsaturation remaining after hydrogenation is less than 5 percent of the starting level of unsaturation, and preferably less than 3 percent of the original.
  • Statistical copolymers of styrene and butadiene, also known as styrene-butadiene rubber, or SBR may be used.
  • the copolymer may be hydrogenated by methods known in the art, such as hydrogen gas in the presence of catalysts such as Raney Nickel, and platinum or palladium metals.
  • the diimide reduction described in the examples may also be employed to produce materials that are useful as ion-conducting membranes.
  • Hydrogenated statistical copolymers of styrene and butadiene are also commercially available. Oxidation of residual unsaturated sites in the polymer at levels greater than 5 percent unsaturation leads to degradation of the polymer and shortens the useful life of the membrane under operating conditions.
  • the hydrogenation level may be determined by the method of Parker et al.
  • the percent hydrogenation is calculated using the following equation:
  • a sulfonation process for styrene copolymers is described in US Patent Nos. 5,468,574, 5,679,482, and 6,110,616.
  • the preferred level of sulfonic acid functionality ranges from about one functional group per five aromatic rings (20 mol%) to about four functional groups per five aromatic rings (80 mol%), such that the equivalent weight of the resulting sulfonated polymer is from about 100 grams/sulfonate equivalent to about 1000 grams/sulfonate equivalent.
  • Equivalent weight may be further limited to 400-700, and even further limited to 520-690.
  • the sulfonation level of the polymer may be controlled by the stoichiometric ratio of the sulfonating agent, acetyl sulfate, to the styrene content of the polymer. For example, addition of 1.0 equivalents of acetyl sulfate yields a polymer of 32 mol% sulfonation and 1.4 equivalents yields 44 mol% sulfonation.
  • the HUX membrane is a hydrocarbon hydrophilic polymer that possesses a low equivalent weight, from 1000 down to 100, preferably 700 down to 300 and most preferably 690 down to 380.
  • Partially sulfonated styrehe-olefin copolymers are generally preferred. Specifically, styrene-ethylene and styrene-hydrogenated butadiene, isoprene or equivalent olefinic copolymers that possess a random, alternating, segmented or statistical in monomer distribution along the chain are preferred.
  • Pseudo-random is a subclass of statistical; a weighted change in the monomer incorporation that skews the distribution from a random arrangement (i.e.
  • Bernoullian is defined as statistical. Linear arrangements have been described here, but branched or grafted including star arrangements of monomers are possible as well.
  • block copolymers of styrene and hydrogenated butadiene, isoprene, or equivalent olefin can be employed.
  • the block architecture can be diblock, triblock, graft-block, multi-arm starblock, multiblock, segmented or tapered block.
  • the HUX support material is preferably, but not limited to, a polyolefin, spaced- member, fiber netting. Fiber extrusion followed by melt bonding is a common method to prepare the netting, however, other methods can be used by themselves or in combination. These include injection molding, compression molding, fiber extrusion with solvent bonding, spin bonding, and ultrasonic welding.
  • Suitable materials for the reinforcing substrate include woven, nonwoven, knit and cross-laid fabrics; in the context of the present invention, the term 'fabrics' is defined as including meshes and nettings. Microporous films may also be used.
  • the fabric of a reinforcing substrate may be composed of synthetic fibers or filaments, glass yarns, non- corroding metal fibers, such as nickel fibers, or carbon fibers.
  • the fibers, filaments or yarns should be ones to which the water-conducting polymer film, adheres strongly.
  • Suitable synthetic fibers include polyolefins, particularly polyethylene or polypropylene, and polyesters.
  • the fibers may have organic or inorganic sizing agents or coupling agents applied, including polyvinylalcohol, starches, oil, polyvinylmethylether, acrylic, polyester, vinylsilane, aminosilane, titanate, and zirconate. Silicone-based lubricants are sometimes employed for greater tear strength.
  • a microporous film may be composed of any synthetic polymer to which the humidity-conducting polymer adheres.
  • the films may have a polyolefin composition, and more particularly, polyethylene. Films having a fluoropolymer composition may also be used.
  • a composite membrane for use in a humidity exchange cell according to the present invention may be prepared by impregnating the substrate with a humidity-conducting polymer.
  • Sequential buildup facilitates the manufacturing of the overall composite; coating is typically continued until a homogenous sheet is formed when reinforcement may or may not be completely coated. Formulations that readily wet the substrate are available at low cost and produce composites without holes or other defects are preferred.
  • the water-conducting polymer may be applied to the reinforcing substrate by hot roll laminating it with reinforcing substrate, thus eliminating the need for multiple coating passes.
  • the water-conducting polymer film may also contain a ceramic filler, if desired.
  • a composite membrane composed of nonwoven fabric may be manufactured by adding staple-pulped fiber to solution of the water conducting polymer, and coating on a release substrate.
  • the humidity-conducting polymer may contain one or more additives, including crosslinking agents, flame retardants (suppressants and synergists), biocides (mildewicides, fungicides, anti-mold- agents, antiviral agents, bacteriocides, anti-parasitic agents, and insecticides.), plasticizers, uv stabilizers (uv absorbers, and light stabilizers), antioxidants (primary or secondary) and thermal stabilizers. Any one compound may impart one or more characteristic enhancements.
  • the basic requirements are that (a) the additive is miscible with the hydrophilic polymer, (b) it does not compromise the mechanical strength or integrity of the membrane in the cell, (c) it not reduce the performance (e.g.
  • Compatible chemical agents are 10,10'-oxybisphenoxarsine available from Rohm and Haas in a liquid or resin carrier under the tradname Vinyzene.
  • An arsenic-free alternative is 4-chloro-3,5- dimethyl phenol an organic chemical available from Aldrich. These can be used effectively at loadings up to 5.0 phr.
  • Dow Chemical's fungicide AMICAL 48 and bactericide BIOPAN BP PLUS, both toxic metal-free are preferred.
  • Flame retardancy is important insofar as additives can reduce the tendency of the cell to catch fire, spread a fire and to reduce smoke emissions.
  • a non-halogen flame retardant (basically a flame inhibitor) is typically used for polyolefins. This is available from Unitex chemical under the tradename Uniplex FRX 44-94S. Bromine-containing retardants, Uniplex BAP-755 (brominated alkyl phosphate) and Uniplex FRP-64 (poly (2,6-dibromophenylene oxide)) are also viable.
  • the polymeric, flame retardant is desirable but it requires a synergist, for which the high phosphorous- containing FRX 44-94S is suitable.
  • Great Lakes Chemicals' tetrabromobisphenol A is preferred for polymer solubility.
  • Organophosphates serve as hydrophilic plasticizers that function by increasing the water or some other highly polar liquid retention of the membrane in HUX cell in the application environment.
  • the increased water or some other highly polar liquid content may improve performance by increasing membrane permeability as well as reduce flammability, since substantially more water or some other highly polar liquid must evaporate before flames may spread to the cell.
  • the evaporation of water or some other highly polar liquid suppresses smoke.
  • these can potentially function as synergists for bromine-containing flame retardants.
  • trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate and tris(2-ethyl hexyl) phosphate.
  • Antioxidants can increase shelf life of HUX cells by circumventing the auto-oxidation of the hydrophilic polymer during storage.
  • a more important advantage is the ability to reduce oxidation of the sulfonated hydrophilic polymer in the HUX cell during operation since at low humidity the polymer is continuously subject to the transfer of heat and thus, will see temperatures as high as 37°C. Oxidation of organic impurities may result and reduce performance this be minimized with the use of antioxidants.
  • BNX 1076 stearyl-3-(3',5'-di-tert-butyl-4-hydroxyphenyl) propionate
  • BNX 1010 tetrakis[methylene-3 (3',5'-di-tert-butyl-4-hydroxyphenyl)propionate] methane
  • HRJ-12700 poly(phenol-formaldehyde) novalac resin
  • Peroxide decomposers add benefit as synergists to hindered phenols, these are aryl phosphites; such as Tris(2,4-ditert-butylphenyl) phosphite (Benafos 1680).
  • UV stabilizers are important for outdoor applications; these are light absorbers with a broad absorption range of which benzotriazoles are preferred.
  • Ciba's Tinuvin 384-2 Benzene propionic acid (3-2H-benzotriazol-2-yl)-5-(1,1-di-methylethyl-4)-hydroxy, C7-C9-branched and linear alkyl esters) is suitable because of good thermal and environmental stability.
  • Hindered amine light stabilizers may be suitable. However, free amines form salts that may reduce water or some other highly polar liquid transport, these are less preferred. Therefore, nitroso-alkyl and specifically nitroso-alkyl ethers containing HALS are preferred for these polymers to maximize their effectiveness as stabilizers.
  • the first approach is small molecule coupling of two chains through polymeric chain radicals.
  • the polymeric chain radicals are created by reaction of olefinic (or styrenic) units with primary radicals (formed from the thermal decomposition of peroxides, or created by scission and/or ionization of the olefinic units by UV, e-beam, gamma-ray, high energy particles.
  • the polymeric chain radicals form bonds to maleimide by addition to double bonds or by radical coupling. Reaction of two such chains with the single molecule forms a crosslink.
  • N,N'-1,3-Phenylene-dimaleimide is a preferred example.
  • Peroxide initiators are benzoyl peroxide, 1,1-Di-(tert-butylperoxy)-3,3,5- trimethylcyclohexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyns-3.
  • the initiator type functionality, primary radical reactivity, initiation efficiency, coupling or crosslinking agent type; crosslinking mechanism, specific interaction with polymer, microstructure of the polymer; reactivity of polymer radical, mobility and concentration of radicals which is controlled for the most part by temperature and/or where applicable the light intensity for photoinitiation or photosensitization.
  • Organometallic crosslinking agents of the enolate-type also fare well when used in conjunction with the more reactive alkyl peroxides as initiators.
  • the more stable benzoyl and isobutyrl peroxide radicals tend to have low initiation efficiencies for crosslinking but if high concentrations of initiator can be achieved by increasing solubility in the polymer then these can be suitable.
  • Organometallic agents of chelated metals that possess multiple stable oxidation states are promising, such as metal diketonates or derivatives thereof. Aluminum acetoacetonate is a preferred example.
  • the metals are redox-active in the chelated state, these can potentially catalyze decomposition of peroxides or serve as photoactivators or sensitizers for photoinitiators.
  • Useful peroxide initiators are benzoyl peroxide, 1,1-Di-(tert-butylperoxy)-3,3,5- trimethylcyclohexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3. These can crosslink in conjunction with other agents or alone with heat, ultraviolet, visible light, e- beam, high energy particle bombardment, such, alpha particles, ionizing radiation such as gamma rays and by electric discharge such as plasma.
  • the list includes but is not limited to: initiators; 1,1-Di-(tert-butylperoxy)-3,3,5- trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, rheta-chloroperoxybenzoic acid, benzoyl peroxide; crosslinking agents (includes coupling agents); aluminum acetylacetonate, cobalt(lll) acetylacetonate, cobalt(ll) acetylacetonate, nickel ketene acetals, N,N'-1,3- phenylene-dimaleimide, divinyl sulfone, trispropargyl benzene, divinyl benzene, vinyl triethoxy silane, hexamethyld
  • the second approach is sulfonamide crosslinking.
  • the reaction of sulfonyl-imidazole or equivalent with aromatic amines results in sulfonamide linkage between styrene units.
  • the reaction of a styrene sulfonic acid unit of the polymer chain with 1,1'-carbonyl diimidazole forms styrene sulfonyl imidazole.
  • the imidazole molecule is a good leaving group so even moderate nucleophiles such as, aromatic diamines displace them.
  • a suitable aromatic diamine is 4-aminophenylsulfone.
  • crosslinking agents may be added to a solution of the polymer, mixed in, and cast normally. Subsequently the HUX cell may be dried in an oven to remove residual solvent, heated in an oven, or exposed to radiation. It is an object of the invention that the additives be simply incorporated into the formulation.
  • FIG. 2 is a partially exploded view of a humidity exchange cell or ventilator core 20 including a composite membrane 10, a first chamber 22 for containing a first fluid, a second chamber 24 for containing a second fluid and a number of spacers or ribs 6 which are adhered to membrane 10.
  • Cell 20 includes a series of alternating first and second chambers.
  • a cap 26 may be used to enclose the topmost and/or bottommost chambers.
  • the membranes 10 are stacked one on top of another to form ventilator core 20 as shown in FIG 2.
  • the orientation of the each layer is rotated by 90 degrees as it is put down into the core. This forms the cross-flow pattern for the exchange of heat and moisture within the core.
  • Not shown, but fully realizable, is a counter-flow arrangement of the layers.
  • the layers would be in a single orientation, with no rotation, in the core.
  • a complex manifold would be designed to route gas streams to every other layer in the stack. These manifolds would be placed on opposite sides of the core. The non- manifolded sides of the core could be sealed to the external environment if necessary.
  • Spacer 16 as shown in FIGS.
  • spacer 16 may be a corrugated paper or plastic sheet.
  • spacer 16 may be a series of adhesive beads.
  • the adhesive may be a hot-melt, cold-melt, or solid adhesive; it may be either thermoplastic or thermosetting.
  • the HUX cell may possess certain specific sub-elements to be effective as a mass (i.e. moisture) exchanger.
  • the basic sub-elements are as follows: (a) a hydrocarbon hydrophilic polymer membrane formulated to be highly permeable to water or some other highly polar liquid or gas, (b) a support matrix to impart mechanical integrity to the membrane and to maintain planarity during operation and (c) a manifold for the distribution of a fluid across the face of the membrane.
  • the disclosed HUX cell is of unitary design in that it incorporates all three sub-elements into a complete cell structure that can be fabricated as a single unit. The device can be built up of this structure by simple stacking and securing the cells in an enclosure.
  • a cross-flow sensible and latent heat exchanger was constructed.
  • the membranes in the exchanger were made by laminating a nylon non-woven reinforcement to a layer of a sulfonated styrene-olefin polymer.
  • the membranes were stacked on top of one another using a PVC spacer with an applied adhesive.
  • the PVC spacers were oriente at 90 degrees to each other on alternating layers. Every other layer in the core had the same flow direction: 1 , 3, 5, 7 etc. had the same flow direction while 2, 4, 6, 8, etc. had a flow direction that was oriented 90 degrees.
  • the edges of each layer in the core were sealed with double-sided adhesive tape.
  • the cross-flow exchanger was placed in a test apparatus where the flow rate, temperature, and moisture of two airflows could be controlled.
  • One air flow had approximately a 90 °F temperature at a relative humidity of 55% of saturation.
  • the other airflow was held at 70 °F and a relative humidity of 50% of saturation.
  • the exchange of sensible and latent heat between the two airflows at different airflow rates was monitored.
  • the data in graph form is shown in FIG. 3.
  • the airflow is expressed is normalized as a function of the square feet of membrane area. This allows us to compare exchangers of various materials and exchangers against each other using the exchange area within the exchanger.
  • the graph shows that over 70% total effectiveness for this type of exchanger can be achieved using sulfonated styrene-olefin polymer membranes.

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Abstract

L'invention concerne une cellule d'échange d'humidité unitaire (HUX) comportant au moins une membrane composite (10) disposée entre au moins une première chambre (22) destinée à recevoir un courant d'un premier fluide, et au moins une deuxième chambre (24) destinée à recevoir un courant d'un deuxième fluide. Ladite membrane composite (10) est constituée d'un polymère conducteur d'humidité au moins partiellement sulfoné, comportant des résidus d'au moins un monomère arylvinyle, et d'un substrat de renforcement lié à ladite membrane. La cellule selon l'invention trouve son application dans divers procédés physiques et chimiques, et dans des dispositifs faisant intervenir le transfert, l'échange, l'extraction, et la distribution d'humidité ou d'autres liquides ou gaz très polaires. Ladite cellule trouve notamment son application dans le ventilateur de récupération d'énergie à membrane (MERV) dans lequel de la chaleur et de l'humidité sont transférés entre deux courants d'air, un courant d'entrée et un courant de sortie, dans un immeuble climatisé.
PCT/US2002/007709 2001-03-13 2002-03-13 Dispositif d'echange de chaleur et d'humidite WO2002072242A1 (fr)

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JP2002571197A JP2004535270A (ja) 2001-03-13 2002-03-13 熱及び水分の交換装置
GB0321274A GB2389063A (en) 2001-03-13 2002-03-13 Heat and moisture exchange device
CA002440961A CA2440961A1 (fr) 2001-03-13 2002-03-13 Dispositif d'echange de chaleur et d'humidite

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100439849C (zh) * 2004-02-10 2008-12-03 三菱电机株式会社 温度湿度交换器
US8263713B2 (en) 2009-10-13 2012-09-11 Kraton Polymers U.S. Llc Amine neutralized sulfonated block copolymers and method for making same
US8377514B2 (en) 2008-05-09 2013-02-19 Kraton Polymers Us Llc Sulfonated block copolymer fluid composition for preparing membranes and membrane structures
US8445631B2 (en) 2009-10-13 2013-05-21 Kraton Polymers U.S. Llc Metal-neutralized sulfonated block copolymers, process for making them and their use
EP2618090A1 (fr) 2012-01-20 2013-07-24 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur thermique et procédé de production
WO2015006856A1 (fr) 2013-07-19 2015-01-22 Marcel Riendeau Élément d'échangeur de chaleur/enthalpique et procédé de fabrication associé
EP2829834A1 (fr) 2013-07-22 2015-01-28 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur d'enthalpie et procédé de production
EP2829836A1 (fr) 2013-07-22 2015-01-28 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur d'enthalpie et procédé de production
US9365662B2 (en) 2010-10-18 2016-06-14 Kraton Polymers U.S. Llc Method for producing a sulfonated block copolymer composition
US9394414B2 (en) 2010-09-29 2016-07-19 Kraton Polymers U.S. Llc Elastic, moisture-vapor permeable films, their preparation and their use
WO2016116806A1 (fr) 2015-01-23 2016-07-28 Zehnder Group International Ag Élément d'échangeur enthalpique, échangeur enthalpique comportant de tels éléments et leur procédé de production
US9429366B2 (en) 2010-09-29 2016-08-30 Kraton Polymers U.S. Llc Energy recovery ventilation sulfonated block copolymer laminate membrane
US9861941B2 (en) 2011-07-12 2018-01-09 Kraton Polymers U.S. Llc Modified sulfonated block copolymers and the preparation thereof
EP3276292A1 (fr) 2016-07-25 2018-01-31 Zehnder Group International AG Élément échangeur enthalpique, échangeur enthalpique comprenant de tels éléments et leur procédé de production
US9887042B1 (en) 2013-03-26 2018-02-06 Ehrenberg Industries Corporation Dielectric material, capacitor and method
US10436475B2 (en) 2013-12-02 2019-10-08 Zehnder Group International Ag System and method for fastening a heating or cooling body
US11759753B2 (en) 2017-07-24 2023-09-19 Zehnder Group International Ag Enthalpy exchanger element, enthalpy exchanger comprising such elements and method for their production

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003903507A0 (en) 2003-07-08 2003-07-24 U. S. Filter Wastewater Group, Inc. Membrane post-treatment
US8222346B2 (en) 2003-09-23 2012-07-17 Dais-Analytic Corp. Block copolymers and method for making same
JP4206894B2 (ja) * 2003-10-15 2009-01-14 三菱電機株式会社 全熱交換素子
US20050158198A1 (en) * 2003-12-21 2005-07-21 Albers Walter F. Micro-cycle energy transfer systems and methods
ATE523240T1 (de) 2004-07-05 2011-09-15 Siemens Water Tech Corp Hydrophile membranen
WO2006017245A2 (fr) * 2004-07-12 2006-02-16 Aegis Biosciences, Llc Polymeres de styrene sulfones pour articles medicaux et dispositifs de voiles barrieres
CN100487003C (zh) * 2004-12-21 2009-05-13 比亚迪股份有限公司 一种聚合物及含有该聚合物的质子交换膜
US20060147773A1 (en) * 2005-01-06 2006-07-06 Steinshnider Jeremy D Heat and humidity exchanger
TWI326691B (en) 2005-07-22 2010-07-01 Kraton Polymers Res Bv Sulfonated block copolymers, method for making same, and various uses for such block copolymers
US7320361B2 (en) 2005-10-28 2008-01-22 Mitsubishi Denki Kabushiki Kaisha Heat exchanger
JP5435942B2 (ja) 2006-05-29 2014-03-05 電気化学工業株式会社 クロス共重合体の製造方法、得られるクロス共重合体、及びその用途
KR100737695B1 (ko) * 2006-06-28 2007-07-09 이찬봉 개선된 라이너를 갖는 전열소자
WO2008037079A1 (fr) * 2006-09-29 2008-04-03 Dpoint Technologies Inc. Échangeur de chaleur et d'humidite plissé avec des éléments à champ d'écoulement
WO2008089484A1 (fr) * 2007-01-20 2008-07-24 Dais Analytic Corporation Transfert de masse sélectif à phases multiples à travers une membrane
CN101918487A (zh) * 2007-06-26 2010-12-15 艺杰斯生物科学有限责任公司 稳定且相容的聚合物共混物
US7824766B2 (en) * 2007-11-20 2010-11-02 Energy Wall, Llc Sorption paper and method of producing sorption paper
WO2009094032A1 (fr) * 2008-01-25 2009-07-30 Midwest Research Institute Refroidisseur par évaporation indirecte utilisant un dessiccatif liquide contenu dans une membrane pour la déshumidification
WO2010132983A1 (fr) 2009-05-18 2010-11-25 Dpoint Technologies Inc. Membranes revêtues pour l'échange enthalpique et d'autres applications
US9393557B2 (en) 2010-01-09 2016-07-19 Dais Analytic Corporation Anionic exchange electrolyte polymer membranes
US8800308B2 (en) 2010-05-25 2014-08-12 7Ac Technologies, Inc. Methods and systems for desiccant air conditioning with combustion contaminant filtering
CN104096459B (zh) 2010-09-07 2018-05-11 戴斯分析公司 使用选择性传递膜的流体处理系统和方法
EP2673587A1 (fr) * 2011-02-09 2013-12-18 Klingenburg GmbH Élément d'échange de chaleur et/ou d'humidité
US9541302B2 (en) * 2011-06-03 2017-01-10 3M Innovative Properties Company Flat panel contactors and methods
CA2841544A1 (fr) * 2011-07-14 2013-01-17 Dow Global Technologies Llc Films de transport selectif de gaz comportant des copolymeres bromes de styrene-butadiene
EP2742557B1 (fr) * 2011-08-11 2016-10-12 MAHLE Behr GmbH & Co. KG Dispositif pour thermoréguler un accumulateur d'énergie en particulier pour un véhicule et procédé de fabrication de celui-ci
US11021559B2 (en) 2011-10-31 2021-06-01 Kraton Polymers Llc Sulfonated block copolymer laminates with polar or active metal substrates
US20130108880A1 (en) * 2011-10-31 2013-05-02 Kraton Polymers U.S. Llc Sulfonated block copolymer laminates with polar or active metal substrates
US9293269B2 (en) 2012-02-08 2016-03-22 Dais Analytic Corporation Ultracapacitor tolerating electric field of sufficient strength
WO2013157045A1 (fr) 2012-04-20 2013-10-24 三菱電機株式会社 Élément d'échange de chaleur
US9101874B2 (en) 2012-06-11 2015-08-11 7Ac Technologies, Inc. Methods and systems for turbulent, corrosion resistant heat exchangers
US9868834B2 (en) 2012-09-14 2018-01-16 Evoqua Water Technologies Llc Polymer blend for membranes
EP2929256A4 (fr) 2012-12-04 2016-08-03 7Ac Technologies Inc Méthodes et systèmes de refroidissement de bâtiments avec des charges thermiques élevées grâce à des refroidisseurs à dessiccant
ES2683855T3 (es) 2013-03-01 2018-09-28 7Ac Technologies, Inc. Sistema de aire acondicionado desecante
US9140460B2 (en) 2013-03-13 2015-09-22 Alliance For Sustainable Energy, Llc Control methods and systems for indirect evaporative coolers
US9140471B2 (en) 2013-03-13 2015-09-22 Alliance For Sustainable Energy, Llc Indirect evaporative coolers with enhanced heat transfer
KR20150119345A (ko) 2013-03-14 2015-10-23 7에이씨 테크놀로지스, 아이엔씨. 액체 흡수제 공조 시스템 개장을 위한 방법 및 시스템
US20140260399A1 (en) 2013-03-14 2014-09-18 7Ac Technologies, Inc. Methods and systems for mini-split liquid desiccant air conditioning
ES2759926T3 (es) 2013-06-12 2020-05-12 7Ac Tech Inc Sistema de aire acondicionado desecante líquido
CN114935180B (zh) 2014-03-20 2023-08-15 艾默生环境优化技术有限公司 空气调节系统、冷却和除湿的方法和加热和加湿的方法
JP6443246B2 (ja) * 2014-07-15 2018-12-26 王子ホールディングス株式会社 全熱交換器エレメント用原紙、およびその製造方法
FR3024533B1 (fr) * 2014-07-31 2016-08-26 Commissariat Energie Atomique Echangeur enthalpique ameliore
EP3221648B1 (fr) 2014-11-21 2020-01-08 7AC Technologies, Inc. Système de climatisation à déshydratant liquide
CZ2014956A3 (cs) * 2014-12-23 2016-05-18 2Vv S.R.O. Entalpický výměník tepla
US10322375B2 (en) 2015-07-14 2019-06-18 Evoqua Water Technologies Llc Aeration device for filtration system
DE102016210478A1 (de) * 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
DE102016210484A1 (de) * 2016-06-14 2017-12-14 Evonik Degussa Gmbh Verfahren zur Entfeuchtung von feuchten Gasgemischen
EP3704416B1 (fr) 2017-11-01 2023-04-12 Emerson Climate Technologies, Inc. Procédés et appareil de distribution uniforme de déshydratant liquide dans des modules de membrane dans des systèmes de climatisation à déshydratant liquide
EP3704415A4 (fr) 2017-11-01 2021-11-03 7AC Technologies, Inc. Système de réservoir pour système de conditionnement d'air à déshydratant liquide
US11022330B2 (en) 2018-05-18 2021-06-01 Emerson Climate Technologies, Inc. Three-way heat exchangers for liquid desiccant air-conditioning systems and methods of manufacture
CN111561706B (zh) * 2020-05-11 2022-01-25 大唐环境产业集团股份有限公司 一种一体式气体除液及水热回收装置与方法
CN111533865B (zh) * 2020-05-20 2022-07-05 青岛大学 一种抗蛋白吸附自清洁嵌段共聚物、制备方法及其应用
US11391487B2 (en) 2020-09-17 2022-07-19 Bradford D Wallace Air to air cross flow heat and moisture exchanger

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2287933A1 (fr) * 1974-10-15 1976-05-14 Rhone Poulenc Ind Intercalaire pour appareil a membrane
EP0442677A2 (fr) * 1990-02-12 1991-08-21 Praxair Technology, Inc. Procédé de déshydratation de gaz
US6110616A (en) * 1998-01-30 2000-08-29 Dais-Analytic Corporation Ion-conducting membrane for fuel cell
US6145588A (en) * 1998-08-03 2000-11-14 Xetex, Inc. Air-to-air heat and moisture exchanger incorporating a composite material for separating moisture from air technical field
EP1052458A2 (fr) * 1999-05-10 2000-11-15 Mitsubishi Denki Kabushiki Kaisha Echangeur de chaleur et sa méthode de fabrication
WO2002009850A2 (fr) * 2000-07-28 2002-02-07 Dais Analytic Corporation Membranes de transport d'eau et d'ions et leurs utilisations

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5579996A (en) * 1978-12-14 1980-06-16 Teijin Ltd Wet heat exchanger
US4797190A (en) * 1986-10-06 1989-01-10 T And G. Corporation Ionic semiconductor materials and applications thereof
EP0326083B1 (fr) * 1988-01-26 1994-06-01 Asahi Glass Company Ltd. Membrane permseléctif de vapeur
US5468574A (en) * 1994-05-23 1995-11-21 Dais Corporation Fuel cell incorporating novel ion-conducting membrane
JPH1054691A (ja) * 1996-08-08 1998-02-24 Mitsubishi Electric Corp 熱交換器の間隔板及び熱交換器用部材及び熱交換器並びにその製造方法
US6233824B1 (en) * 1999-10-08 2001-05-22 Carrier Corporation Cylindrical heat exchanger

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2287933A1 (fr) * 1974-10-15 1976-05-14 Rhone Poulenc Ind Intercalaire pour appareil a membrane
EP0442677A2 (fr) * 1990-02-12 1991-08-21 Praxair Technology, Inc. Procédé de déshydratation de gaz
US6110616A (en) * 1998-01-30 2000-08-29 Dais-Analytic Corporation Ion-conducting membrane for fuel cell
US6145588A (en) * 1998-08-03 2000-11-14 Xetex, Inc. Air-to-air heat and moisture exchanger incorporating a composite material for separating moisture from air technical field
EP1052458A2 (fr) * 1999-05-10 2000-11-15 Mitsubishi Denki Kabushiki Kaisha Echangeur de chaleur et sa méthode de fabrication
WO2002009850A2 (fr) * 2000-07-28 2002-02-07 Dais Analytic Corporation Membranes de transport d'eau et d'ions et leurs utilisations

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100439849C (zh) * 2004-02-10 2008-12-03 三菱电机株式会社 温度湿度交换器
US8377514B2 (en) 2008-05-09 2013-02-19 Kraton Polymers Us Llc Sulfonated block copolymer fluid composition for preparing membranes and membrane structures
US8263713B2 (en) 2009-10-13 2012-09-11 Kraton Polymers U.S. Llc Amine neutralized sulfonated block copolymers and method for making same
US8445631B2 (en) 2009-10-13 2013-05-21 Kraton Polymers U.S. Llc Metal-neutralized sulfonated block copolymers, process for making them and their use
US9394414B2 (en) 2010-09-29 2016-07-19 Kraton Polymers U.S. Llc Elastic, moisture-vapor permeable films, their preparation and their use
US9429366B2 (en) 2010-09-29 2016-08-30 Kraton Polymers U.S. Llc Energy recovery ventilation sulfonated block copolymer laminate membrane
US9365662B2 (en) 2010-10-18 2016-06-14 Kraton Polymers U.S. Llc Method for producing a sulfonated block copolymer composition
US9861941B2 (en) 2011-07-12 2018-01-09 Kraton Polymers U.S. Llc Modified sulfonated block copolymers and the preparation thereof
KR20130085929A (ko) 2012-01-20 2013-07-30 쩬더 페어카우프스- 운트 페어발퉁스 아게 열 교환기 소자 및 그 제조방법
US10012450B2 (en) 2012-01-20 2018-07-03 Westwind Limited Heat exchanger element and method for the production
RU2618736C2 (ru) * 2012-01-20 2017-05-11 Вествинд Лимитед Элемент теплообменника и способ для производства
WO2013107554A1 (fr) 2012-01-20 2013-07-25 Zehnder Verkaufs- Und Verwaltungs Ag Élément d'échangeur de chaleur et procédé pour sa production
EP2618090A1 (fr) 2012-01-20 2013-07-24 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur thermique et procédé de production
US9887042B1 (en) 2013-03-26 2018-02-06 Ehrenberg Industries Corporation Dielectric material, capacitor and method
WO2015006856A1 (fr) 2013-07-19 2015-01-22 Marcel Riendeau Élément d'échangeur de chaleur/enthalpique et procédé de fabrication associé
US10415900B2 (en) 2013-07-19 2019-09-17 Westwind Limited Heat / enthalpy exchanger element and method for the production
WO2015011544A1 (fr) 2013-07-22 2015-01-29 Zehnder Group International Ag Élément d'échangeur enthalpique et son procédé de fabrication
EP3620743A1 (fr) 2013-07-22 2020-03-11 Zehnder Group International AG Élément d'échangeur d'enthalpie et procédé de production
EP3620742A1 (fr) 2013-07-22 2020-03-11 Zehnder Group International AG Élément d'échangeur d'enthalpie et procédé de production
WO2015011543A1 (fr) 2013-07-22 2015-01-29 Zehnder Group International Ag Élément d'échangeur enthalpique et son procédé de fabrication
US10041746B2 (en) 2013-07-22 2018-08-07 Zehnder Group International Ag Enthalpy exchanger element and method for the production
EP2829836A1 (fr) 2013-07-22 2015-01-28 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur d'enthalpie et procédé de production
EP2829834A1 (fr) 2013-07-22 2015-01-28 Zehnder Verkaufs- und Verwaltungs AG Élément d'échangeur d'enthalpie et procédé de production
US10436475B2 (en) 2013-12-02 2019-10-08 Zehnder Group International Ag System and method for fastening a heating or cooling body
KR20170104607A (ko) * 2015-01-23 2017-09-15 젠더 그룹 인터내셔널 아게 엔탈피 교환기 요소, 그러한 요소를 포함하는 엔탈피 교환기 및 이들을 제조하기 위한 방법
WO2016116806A1 (fr) 2015-01-23 2016-07-28 Zehnder Group International Ag Élément d'échangeur enthalpique, échangeur enthalpique comportant de tels éléments et leur procédé de production
KR102455119B1 (ko) * 2015-01-23 2022-10-14 젠더 그룹 인터내셔널 아게 엔탈피 교환기 요소, 그러한 요소를 포함하는 엔탈피 교환기 및 이들을 제조하기 위한 방법
WO2018020392A1 (fr) 2016-07-25 2018-02-01 Zehnder Group International Ag Élément de roue hydroscopique, roue hydroscopique comprenant de tels éléments et leur procédé de production
EP3276292A1 (fr) 2016-07-25 2018-01-31 Zehnder Group International AG Élément échangeur enthalpique, échangeur enthalpique comprenant de tels éléments et leur procédé de production
US11759753B2 (en) 2017-07-24 2023-09-19 Zehnder Group International Ag Enthalpy exchanger element, enthalpy exchanger comprising such elements and method for their production

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CN101022879A (zh) 2007-08-22
JP2004535270A (ja) 2004-11-25
GB2389063A (en) 2003-12-03
US20030106680A1 (en) 2003-06-12
GB0321274D0 (en) 2003-10-08
CA2440961A1 (fr) 2002-09-19

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