CN101022879A - Heat and moisture exchange device - Google Patents

Heat and moisture exchange device Download PDF

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Publication number
CN101022879A
CN101022879A CNA028098609A CN02809860A CN101022879A CN 101022879 A CN101022879 A CN 101022879A CN A028098609 A CNA028098609 A CN A028098609A CN 02809860 A CN02809860 A CN 02809860A CN 101022879 A CN101022879 A CN 101022879A
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polymer
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composite membrane
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约瑟夫·M.·塞尔皮科
斯科特·埃伦贝格
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Days Inn - Co Analysis
Dais Analytic Corp
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    • 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
    • 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
    • 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

Abstract

A unitary humidity exchange cell (HUX) is disclosed that includes 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. The composite membrane include an at least partially sulfonated humidity-conducting polymer comprising residues derived from at least one arylvinyl monomer; and a reinforcing substrate bonded thereto. The product finds utility in a variety of physical and chemical processes and products whereby moisture or other highly polar liquid or gas transfer, exchange removal or delivery is important. A notable application is the Membrane Energy Recovery Ventilator (MERV) in which both heat and moisture is transferred between two air streams, one intake and one exhaust, from an air-conditioned building.

Description

The switching equipment of heat and moisture
Technical field
The present invention relates to use composite polymeric film between fluid, to transmit the equipment and the device of heat and water.
Background technology
As its name suggests, monoblock type exchange of moisture element (being HUX) is an equipment component, described equipment can be under the effect of a certain amount of difference that runs through said elements or gradient, and water or other high polar liquid or gas are delivered to opposite side from a side of described element.The operating characteristic of a key of HUX element is the graded that the difference (with respect to environment) of some strength characteristics of this system or range characteristic constitutes described characteristic, thereby impel water or other high polar liquid or gas mass transfer from a side direction opposite side of film, wherein except described water or other high polar liquid or gas, can also follow or not be attended by flowing of electronics, proton, lewis' acid.Under the influence of this characteristic, liquid water or other high polar liquid or gas exchange by described differential permeability film just.The transmission of described water or other high polar liquid or gas can with or enter (or effusion) described logistics without water or other high polar liquid or gas by evaporation, described evaporation adopts heat absorption, adiabatic or other thermodynamics means to carry out; The for example evaporation and the condensation of liquid water or other high polar liquid or gas, or water or other high polar liquid or gas enter a kind of neat liquid stream by simple diffusion.The running through direction and must have a certain amount of limited gradient of described film, for example vapour pressure deficit, osmotic pressure or hydrostatic pressure difference, difference in chemical potential, heat chemistry potential difference, electrochemistry potential difference, magnetochemistry gesture and heat (temperature or enthalpy) potential difference, electrical potential difference, electromagnetism potential difference, thermoelectric potential difference or electric heating potential difference.Two kinds of logistics wherein should be arranged at least, and a kind of logistics offers each surface of described film in some way as liquid or vapor stream, and each logistics is at least in same a kind of difference that exists in nature of system.Water or other high polar liquid or gas system when a logistics is delivered to another logistics is tending towards thermodynamical equilibrium.Orientation relationship among the present invention between logistics can be selected arbitrarily, can be any other form during adverse current and stream, cross-flow, mixed flow or one or more logistics are arranged for how much.The transmission of water or other high polar liquid or gas (for example hydrodynamics, electric hydrodynamics, magnetohydrodynamics, diffusion, migration or convection current) continues to carry out, up to formed gradient be not enough to overcome system the physical chemistry constraint and till being difficult to satisfy the requirement of sustained delivery.In most cases, water or other high polar liquid or the exchange of gas between logistics are slowly, but this may be the limiting factor owing to other, as the influence of effect of boundary layer, concentration polarization, hydrostatic pressure sluggishness, gravity, surface tension effect and convection current or friction.In case yet these engineering designs or systematic influence reach and minimize, and film is to the penetrating power of water or other high polar liquid or gas when strong, inevitably water or other high polar liquid or exchange gas or transmit to speed and control.Therefore a free-revving engine of the present invention is a hydrophilic polymer membrane has strong permeability to water or other high polar liquid or gas, and this is very necessary in many purposes.Described hydrophilic polymer membrane (prescription) must have prop carrier, and must have described two kinds of logistics are provided to described lip-deep device.Second purpose of the present invention is by conventional method described three sub-elements to be assembled into one under low cost.This just requires with the moistening carrier of hydrophilic polymer, and reaching tight contact and showing has excellent combination with it.Therefore, the 3rd purpose of the present invention is that carrier is a kind of polyolefin or polyolefin blend, so that a component of above-mentioned hydrophilic polymer component with carrier on chemical constitution is identical.
The generality of HUX element design is that water (liquid or steam), other high polar substances (liquid or steam) can transmit between any two kinds of fluids.Application example is prevapourising, humidification and the dehumidification of the fuel cell logistics in battery pile and the equipment; Dry gas under pressure; Tertiary oil recovery; Water is as the control of the chemicals production technology of reactant; The separation of mineral in the mining fluid; The industrial separation of oil-water emulsion; Microfiltration and ultrafiltration for purification colloidal suspension and biological organic macromolecule; The water content that in DMFC, keeps methyl alcohol; From salt solution, separate the counter-infiltration of fresh water; Electrolytic cell; Saturating dialysis; Electrodialysis; The saturating dialysis of pressure; Electric osmose and chloro alkaline battery.
Summary of the invention
The present invention relates between the first fluid and second fluid, carry out the element of heat and moisture transmission.Such element comprises at least a composite membrane, described composite membrane be arranged in first chamber of at least one first fluid that is used to flow through and second chamber of second fluid that is used to flow through between; Wherein heat and moisture can transmit between the first fluid and second fluid via composite membrane.Described composite membrane can comprise partly sulfonated at least wet polymer and enhancing base material bonding with it of leading, and wherein said polymer comprises from least a aryl vinyl residues of monomers.Described element also can comprise at least a lip-deep spacer of described composite membrane that is arranged in.Described spacer has the size perpendicular to the composite membrane surface, and the height in this size and first chamber is suitable; The orientation of the longitudinal axis of at least one spacer can be with parallel flowing to of the first fluid in first chamber.The flow direction of the first fluid in first chamber can be perpendicular to the flow direction of second fluid in second chamber, or perhaps in contrast.In some instances, many synthetic polymer rib lines are used as spacer; In other cases, spacer is the pearl of only being made up of adhesive; Also having spacer in addition is the situation of a corrugated plating of being made by paper or plastics.The invention still further relates to the element that contains a plurality of composite membranes and a plurality of first chamber that replaces and second chamber, isolate with composite membrane each other.Enhancing matrix in the described composite membrane can be adhesive-bonded fabric, its by synthetic fibers particularly one or more polyolefin form.Leading wet polymer and can contain a kind of additive in the described composite membrane, described additive is selected from antioxidant, antimicrobial, fire retardant, UV stabilizer, hydrophilic plasticizer and their mixture, particularly contains antioxidant, antimicrobial, fire retardant.Available peroxide initiator and organic metal enolate coupling agent, particularly 1,1-two-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and acetopyruvic acid aluminium, or 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3 and acetopyruvic acid aluminium carry out crosslinked to leading wet polymer.
Brief description
Figure 1 shows that a composite membrane that is used for exchange of moisture element of the present invention.
Fig. 2 is the partial perspective view of exchange of moisture element of the present invention.
Fig. 3 demonstrates and uses exchange of moisture element of the present invention to realize higher heat and moisture transmission.
Detailed Description Of The Invention
Fig. 1 shows a slice composite membrane 10 for moisture exchange component of the present invention. This film bag Draw together the continuous film 12 of leading wet polymer and be incorporated into to intersect the sieve aperture placed and the mode of net Strengthen on the matrix 14. 14 pairs of these films of described enhancing matrix are reinforced so that it can be processed, And make this film bear pressure reduction and not crooked. As shown in Figure 1, be bonded in film 10 surfaces every Arrange along a direction from thing, rib line (or ridge) 16. The opposite side of film is to lead wet polymer 12 smooth surface. The height setting of spacer 16 layer with layer the gap. When spacer leans on When placing the membrane plane at its top, form the air duct of moisture exchange component by its. Describedly lead the copolymer that wet polymer is at least a kind of partial vulcanization, this copolymer comprises Residue from least a aryl vinyl monomer. Correspondingly, described polymer is except containing knot Outside the repetitive of alkene monomer, also contain among the formula II I from aryl among structure formula I and the II The repetitive of vinyl monomer.
Figure A0280986000081
Figure A0280986000082
Figure A0280986000083
R wherein 1, R 2, R 3, R 4Be selected from hydrogen, itrile group, phenyl and low alkyl group respectively; R 5Be hydrogen, chloro or low alkyl group; R 6Be hydrogen or methyl; R 7Be-COOH ,-SO 3H ,-P (O) (OR 8) OH ,-R 9-COOH ,-R 9-SO 3H ,-R 9-P (O) (OR 8) OH; R 8Be hydrogen or low alkyl group; R 9It is the light alkene base; Ar is a phenyl; M, n, 0, q are 0 or the integer of 50-10000.
But described block, grafting or statistical copolymer of leading wet polymer aryl vinyl monomer.United States Patent (USP) 5,468,574; Described some polymer that are suitable in 5,679,482 and 6,110,616, these disclosures are all incorporated by reference at this.Block or graft copolymer contain the quite long homopolymers segment of being made up of comonomer.Correspondingly, term used herein " statistics " is meant the polymer that does not contain long homopolymers segment, to distinguish mutually with block, graft copolymer.Preferred described statistics and convergence thing be no more than 15% more than aryl vinyl total amount in the aryl vinyl monomer block of 3 unit.More preferably, being characterized as of described statistics and convergence thing do not have very high isotacticity or degree of syndiotacticity.Here it is refers at the statistics and convergence thing 13In the C NMR spectrogram, represent the main chain methylene in the identical or different binary sequence of adjacent monomer orientation and the peak area of methine carbon to be no more than 75% of main chain methylene and methine carbon total peak area.
Described statistical copolymer is a well-defined technical term (referring to G.Odian polymerization principle, 1991), and term used herein is with general applied consistent.Statistical copolymer comes from the simultaneous polymerization of two kinds of comonomers, and follows Bernoullian (0 grade of Markov), one-level or secondary Markov statistical model along the distribution of two kinds of monomers of copolymer chain.Can adopt the unsaturated component of free radical, anion, cation or coordination (for example Ziegler-Natta catalyst) initiated polymerization.According to the viewpoint (Pure Appl.Chem., 57,1427,1985) of Ring etc., statistical copolymer is the result of basic process, and these basic processes make the monomeric unit with equal probabilities form statistical series.These processes can form various sequences and distribute, and the arrangement trend of the monomeric unit that wherein has alternately has plenty of the similar units trend and troops, and the then basic demonstration that can't have orderly trend.The Bernoullian statistics comes down to toss a coin statistic law; Distribution through two kinds of monomers in the copolymer of Bernoullian process formation is at random, and it is called as atactic polymer.For example, active end does not have selectivity to styrene or butadiene in fact as styrene or butadiene free radical in radical copolymerization.If so, statistical model will be the Bernoullian model, the copolymer that is obtained will be at random.In most cases the end of the chain in the growth trends towards that one or another kind of monomer is had selectivity.When the end of the chain in the growth is very low to the selectivity of the monomer that adds, can obtain block copolymer by two kinds of synchronous combined polymerizations of monomer, but this situation is seldom.The copolymer that produces among the present invention is classified as block copolymer.
Statistical copolymer demonstrates single glass transition temperature usually.Because existing multiple phase, block and graft copolymer generally to demonstrate multiple glassy state transforms.According to this with statistical copolymer and block and graft copolymer differentiation.Single glass transition temperature reflects the homogeneity of polymer from molecular level.The other result of these homogeneity is, when with electron microscope observation statistical copolymer (as the statistical copolymer of styrene and butadiene), it shows the form of single phase and does not have the separation of microfacies.On the contrary, be example with the block and the graft copolymer of styrene and butadiene, being characterized as of they has two glass transition temperatures, emanates to be styrene enrichment territory and butadiene enrichment territory.Though should be noted that the statistical copolymer for preparing film of the present invention is original according to single glass transition temperature and single phase are arranged, but it may not demonstrate single phase or single glass transition temperature after sulfonation, and this is because polymer of the present invention is subjected to the influence of the physical change that chemical change that sulfonation brings and casting cycle bring.
Be used for the polymerization that wet polymer derives from aryl vinyl of leading of exchange of moisture element of the present invention, describedly naturally lead aryl or the aromatic group that wet polymer can contain suspension.Here the aryl vinyl monomer is defined as containing the monomer of a substituted ethylene base, and the therein ethylene base is replaced by the aryl that aryl, halogen aryl or alkyl replace.The example that contains the monomer of the vinyl that aryl replaces is a styrene, and the example that contains the monomer of the vinyl that the halogen aryl replaces is a chlorostyrene, and the example that contains the monomer of the vinyl that aryl that alkyl replaces replaces is p-octyl group styrene and vinyltoluene.One or more aryl vinyl monomers can carry out combined polymerization with olefin comonomer, and to prepare a kind of polymer that can be sulfonated, resulting sulfonated copolymer can be used for forming the film among the present invention.
Can be used for producing the aryl vinyl monomer that is fit to sulfonated polymers and comprise, for example: all isomers of styrene, vinyltoluene, AMS, t-butyl styrene, chlorostyrene and these compounds.Specially suitable this type of monomer comprises styrene, low alkyl group or its derivative that is replaced by halogen.Preferred monomer comprises styrene, AMS, low alkyl group-(C 1-C 4) or the cinnamic derivative that replaces of phenyl ring, for example adjacent,, styrene, contraposition vinyltoluene or its their mixture of p-methylstyrene, phenyl ring halogenation or the like.Preferred aryl vinyl monomer is a styrene.The residue ratio that derives from vinyltoluene and chlorostyrene derives from the more difficult sulfonation of cinnamic residue; Therefore it is desirable to vinyltoluene and chlorostyrene are used with the aryl vinyl monomer, to obtain the easier residue that is sulfonated, as styrene or AMS, rather than only vinyltoluene and chlorostyrene are used as the aryl vinyl component of polymer.One or more positions are sulfonated the copolymer chain of the sulfonation group that obtains having suspension on the aromatic ring of aryl or aromatic group.
Lead wet polymer and derive from least a aryl vinyl residues of monomers, also can comprise the residue that derives from least one olefinic monomer except that comprising.Preferred olefinic monomer comprises monoolefine such as alpha-olefin, NOL ring alkene and double olefin monomer such as butadiene and isoprene.The C that alpha-olefin comprises ethene and (promptly 1) has ethylene unsaturated bond in the α position 3-10Alkene, as ethene, propylene, butylene and isobutene.Suitable alpha-olefin comprises and contains 3-20 carbon atom, preferred 3-12 carbon atom, the more preferably alpha-olefin of 3-8 carbon atom.Specially suitable is ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, or the one or more combination in ethene and propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene or the 1-octene.These alpha-olefins do not contain aromatic group.Preferred monoene monomer is ethene, propylene, 1-butylene, 2-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene and 1-octene.Preferred NOL ring alkene is the vinyl-ring substitutive derivative of the various isomeries of cycloolefin, and these cycloolefins are: cyclohexene, substituted cyclohexene, ENB, C 1-10Alkyl or C 6-10The ENB (as 5-ethylidene-2-ENB) that aryl replaces.Specially suitable is 1-, 3-and 4 vinyl cyclohexene, ENB and 5-ethylidene-2-ENB.The alpha-olefin of simple straight chain non-branching, as contain the alpha-olefin (as propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene or 1-octene) of 3-20 carbon atom, these are not the example of NOL ring alkene.Preferred aryl groups vinyl statistics and convergence thing is the copolymer of ethylene/styrene, ethylene/propene/styrene, ethylene/styrene/norbornene and ethylene/propene/phenylethylene/norbornene.
Described polymer can also contain the residue that derives from other comonomer (as acrylate monomer).The copolymer (as the copolymer of butadiene and isoprene) that derives from diolefin in addition may contain remaining unsaturated bond.These unsaturated bonds are hydrogenated as last or reduce in sulfonation.In order to be formed for composite membrane of the present invention, described sulfonated copolymer can with other sulfonated copolymer or traditional polyblend.
The wet polymer of leading that is used for exchange of moisture element of the present invention generally contains the cinnamic residue of deriving from of at least 20 weight %.More preferably described copolymer contains the styrene of 20-50 weight %, most preferably contains the styrene of 45 weight %.The scope of the weight average molecular weight of polymer of the present invention (Mw) be 20,000 gram/moles to 1,000,000 gram/mole, preferred 50,000 gram/moles are to 900,000 gram/moles.Sulfonated polymer as film of the present invention is preferably water-insoluble.Water-insoluble when being defined as 100 ℃ the polymer dissolution degree in 100 gram water less than 0.5 gram.The suitable wet polymer of leading comprises the styrene-butadiene statistical copolymer of block styrene-ethene-butylene-styrene copolymer, sulfonation and the reduction of sulfonation, the styrene-ethylene statistical copolymer of sulfonation.The styrene-butadiene statistical copolymer can obtain from Goodyear company; Block styrene-ethene-butylene-styrene copolymer can obtain from Shell company, and styrene-ethylene statistical copolymer (ethylene styrene interpretation (ESI)) can obtain from Dow Chemical. company.Described Dow ESI polymer comprises pseudorandom polymer, as James C.Stevens etc. at EP-A-0,416,815 and Francis J.Timmers at US 5,703, described in 187, wherein both are all incorporated by reference at this.
When diolefin is used as comonomer, before sulfonation is from cinnamic aromatic group, the unsaturated bond in the co-polymer membrane of the present invention is carried out hydrogenation selectively.The numerical value of remaining degree of unsaturation is less than 5% of initial unsaturated level after the hydrogenation, preferably less than initial 3%.Also can use the statistical copolymer (having another name called butadiene-styrene rubber, i.e. SBR) of styrene and butadiene.These copolymers can be with method well known in the prior art (as use hydrogen in the presence of as Raney nickel, platinum or palladium metal catalyst) hydrogenation.The imidodicarbonic diamide reduction of describing in an embodiment can be used for making the raw material of ion-conductive membranes.The also commercially available acquisition of the statistical copolymer of hydrogenated styrene and butadiene.If remaining unsaturated position is greater than 5% of unsaturated level in the polymer, the oxidation meeting causes degraded copolymer and the shortening in the service life of film under service condition.
Utilize the method for Parker etc. can determine the hydrogenation level.By analyzing the FTIR spectrum of hydrogenated styrene butadiene copolymer, measure at 963cm -1And 1493cm -1Peak height (respectively correspondence=CH and-CH 2Absorptance).Utilize following formula to calculate the percentage of hydrogenation:
% hydrogenation=-15.71x+99.4
Wherein x is 963cm -1Peak height and 1493cm -1The ratio of peak height
The sulfonation process of styrol copolymer is at United States Patent (USP) 5,468, is described in 574,5,679,482 and 6,110,616.The preferred levels of sulfonic acid acid functional group is that per functional groups of five aromatic rings (20mol%) are to per four functional groups of five aromatic rings (80mol%), so that the equivalent weight of the sulfonated polymer that produces is 100 gram/sulfonated bodies equivalent to 1000 gram/sulfonated bodies equivalents.For example for a kind of cinnamic copolymer that contains 45 weight %, preferred range is at sulfonic acid group (20mol% of per five styrene units, equivalent weight=1200 gram/equivalents) to four sulfonic acid group of per five styrene units (80mol%, equivalent weight=300 gram/equivalents).Equivalent weight can further be limited in 400-700, and further is limited in 520-690.To containing the cinnamic copolymer of 30 weight %, preferred range is sulfonic acid group (25mo% of per four styrene units, equivalent weight=1400 gram/equivalents) to four sulfonic acid group of per five styrene units (80mol%, equivalent weight=430 gram/equivalents).The sulfonation levels of polymer can recently be controlled by the stoichiometry of styrene-content in sulfonating agent (acetyl sulfate) and the polymer.For example, add the acetyl sulfate output 32mol% sulfonated polymers of 1.0 equivalents, 1.4 equivalents can produce the 44mol% sulfonated polymers.
The HUX film is a kind of hydro carbons hydrophilic polymer, and described hydrophilic polymer has the low equivalent weight of 1000-100, and is preferred 700 to 300, most preferably 690 to 380.Usually preferred partly sulfonated styrene-olefin copolymer.Special optimization styrene-ethene, styrene-hydrogenated butadiene, isoprene or have the equivalent olefin copolymer of the monomer distribution of at random, that replace, segmentation or statistics along strand.The pseudorandom copolymer is the group in the statistical copolymer; The monomer that will depart from distribution because of random alignment is called statistical method in conjunction with the weight change (for example Bernoullian) that causes.Here described linear array, but to arrange also be possible for the branched arrangement of monomer or the grafting that comprises star-arrangement.In addition, also can use the block copolymer of styrene and hydrogenated butadiene, isoprene or equivalent alkene.This segmentation structure can be two sections, three sections, grafting section, multi-arm star section, multistage, broken section or conical section.
The support materials of HUX is (but and unrestricted) a kind of polyolefinic barrier film, fleece preferably.Fiber is extruded and follow-uply is one and produces the common method of this net with melt bonded, but also can be used alone or in combination other method.They comprise that injection moulding, moulded section, fiber are extruded the back solvent bonding, the bonding and ultrasonic bonding of spinning.
The suitable raw material that strengthens base material comprises braiding, nonwoven, knitting and fabric arranged crosswise; Term " fabric " in the scope of the invention " be considered to aperture plate and net.Also can use microporous barrier.The fabric that strengthens base material can be by synthetic fibers, filament, glass fiber, noncorroding metal fiber
(as nickel fiber or carbon fiber) formed.Fiber filaments or yarn should have firm adhesive effect to leading the wet polymer film.Suitable synthetic fibers comprise polyolefin (particularly polyethylene, polypropylene) and polyester.These fibers can contain practical organic or inorganic adhesive or coupling agent, comprise polyvinyl alcohol, starch, oil, polyvinyl methyl ethermaleic anhydride, acrylic resin, polyester, vinyl silanes, amino silane, metatitanic acid fat and zirconic acid fat.For reaching bigger tearing strength, use the lubricant of polysiloxane group sometimes.A microporous membrane can be made up of arbitrary synthetic polymer of leading wet polymer that is stained with.The film that particularly contains polyolefin component, more particularly polyethylene.Also can use the film that contains the fluoropolymer polymer composition.The composite membrane that is used for exchange of moisture element of the present invention can be by preparing with leading wet polymer dipping base material.This can be undertaken by in some known methods any.These methods comprise direct rubbing method, wherein lead wet polymer and are dissolved in The suitable solvent such as the lower alcohol (particularly methyl alcohol or propyl alcohol).Directly the advantage of rubbing method is that it can reduce the number of annex and parts and thereby reduces cost.The low-cost manufacturing is purpose of the present invention.Also can use indirect rubbing method as solution-cast.
Structure in turn is convenient to the manufacturing of whole composite.When the reinforce energy or when can not be complete coated, coating generally be extended to the formation of an even sheet.The preferred preparation that soaks into base material easily can low-costly obtain, and makes the composite of manufacturing not be with hole or other defect.It is provided on the enhancing base material with strengthening the base material hot-roll lamination by leading wet polymer in addition, having saved thus needs the repeatedly requirement of coating.If desired, lead the wet polymer film and can also contain a ceramic filter.At last, add short fibered pulp in the aqueous solution by the guide wet polymer, and it is coated on the separation substrate, make a composite membrane that constitutes by adhesive-bonded fabric.
The described wet polymer of leading can contain one or more additives, as crosslinking agent, fire retardant (inhibitor and synergist), antimicrobial (mould resistant, fungicide, antimycotic agent, antivirotic, bactericide, antiparasitic and pesticide), plasticizer, UV stabilizer (ultraviolet radiation absorption and light stabilizer), antioxidant (elementary or secondary) and heat stabilizer.Any compound can give the raising of one or more performances.Basic demand is: (a) additive and hydrophilic polymer are compatible, and (b) it does not influence mechanical strength or the globality of film in element, and (c) it does not reduce performance (for example moisture transmission efficient) or the life-span of element in application.Therefore these are purpose of the present invention (a, b, c).Though be not purpose of the present invention, preferably when using in preparation with polymer, additive can keep its above-mentioned characteristic active and polymer.
For antimicrobial, because potential lower local pH in the sulfonation hydrophilic polymer, what we mainly paid close attention to is the growth of mould and mildew.Yet also wish to suppress other possible organism such as fungi, bacterium, virus, parasite, insect or protozoan.Must prevent the biotic component of the effective surface area of any reduction logistics moisture transmission film.Compatible chemical reagent is 10,10 '-contain oxygen hexichol oxygen arsenic, it can liquid or the resin carrier mode obtain from Rohm and Haas company, trade mark is Vinyzene.A kind of no arsenic substitute is a 4-chloro-3,5-xylenol (a kind of organic chemicals that can obtain from Aldrich company).They can be used in the load of 5.0phr effectively.Yet, the fungicide AMICAL 48 and the bactericide BIOPAN BP PLUS of preferred Dow Chemical company, both all do not contain toxic metals.
Anti-flammability is important, and flame-retardant additive can prevent that exchange component from catching fire, weakening the trend of fire spread and reduce smog and distribute.Except the low water content steam logistics of air/water or other high polar gas, pure liquid stream does not constitute fire threat.In these are used, a kind of non-halogen fire retardant (being essentially a kind of fire inhibitor) is used for polyolefin.This fire retardant can obtain with trade name Uniplex FRX 44-94S from Unitex chemical company.Suitable fire retardant also has brominated flame-retardant Uniplex BAP-755 (bromo alkylphosphonate) and UniplexFRP-64 (gathering-2,6-dibromobenzene oxidation thing).For reaching high-performance, it is desirable to use the fire retardant of polymerization, but need to cooperate synergist, the FRX44-94S that phosphorus content is high suits for this reason.Yet consider the tetrabromobisphenol A of the preferred Great Lakes of polymer dissolution degree Chemicals company.
Organophosphorus ester can be used as hydrophilic plasticizer, and it works by increasing water or the reservation amount of other high polar liquid in the film of HUX element under environment for use.The water or other the high polar liquid content that increase can improve performance, because can increase permeability of the membrane like this and reduce its combustibility, because in fact more water or other high polar liquid must be evaporated flame can spread to element before.The evaporation of moisture or other high polar liquid has suppressed smog, and simultaneously they have also played the effect of the potential synergist of brominated flame-retardant.Described plasticizer is trialkylphosphate such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate and three (2-ethylhexyl) phosphate.
At lay up period, antioxidant (and heat stabilizer) can prolong the shelf life of HUX element by preventing hydrophilic polymer generation autoxidation.Yet a prior benefit is the oxidation that antioxidant (and heat stabilizer) can reduce sulfonation hydrophilic polymer in the HUX element during operation, because under the low humidity condition, polymer experiences heat transfer continuously and its temperature will be up to 37 ℃.The oxidation meeting produces organic impurities and reduces performance, and this situation can be reduced to Min. by means of antioxidant.Antioxidant be basically some HMWs hindered phenol as: stearoyl-3-(3 ', 5 '-two-tertiary butyl-4-hydroxyphenyl) propionic ester (BNX 1076) and four [methylene-3 (3 ', 5 '-two-tertiary butyl-4-hydroxyphenyl) propionic ester] methane (BNX 1010), both all can obtain from Mayo Corp company.Poly-(P-F) phenolic resins (HRJ-12700) can obtain from Schenectady International company.Peroxide decomposer benefits as the synergist of hindered phenol, and they are that aryl phosphite is as three (2,4-two-tert-butyl-phenyl) phosphite esters (Benafos 1680).Ultra-violet stabilizer is important to outdoor application, and they are the optical absorbing agents with wide absorption region, and preferred ultra-violet stabilizer is a 124 Triazole.Because heat endurance that it is good and environmental stability, the Tinuvin 384-2 of Ciba company (benzenpropanoic acid (3-2H-BTA-2 base)-5-(1,1-two-Methylethyl-4)-hydroxyl, the Arrcostab of the branched and straight chain of C7-C9) is suitable.Hindered amine as light stabilizer (HALS) suits.Yet thereby unhindered amina can form the transmission that salt influences water or other high polar liquid, not preferred such stabilizing agent.Nitroso-the alkane that therefore preferably will contain HALS particularly nitroso alkyl ether is used for these polymer so that its effect maximization as stabilizing agent.
Particularly under saturated (dehydration or hydration) state, when the side (segregation, dehydration, hydration) of film or both sides (infiltration, filter or dialysis) when contacting, crosslinkedly can obtain the further perfect of mechanical strength and integrality by forming at the membrane polymer interchain with liquid water or other high polar liquid.Mainly contain two kinds of cross-linking methods: (a) crosslinked and (b) crosslinked by sulfur-containing group by carbon-containing group.
First method (being type i) is the little molecule couplings of two chains by the polymer chain free radical.Described polymer chain free radical is generated by the reaction of alkene (or styrene) unit and elementary free radical, (described elementary free radical derives from the thermal decomposition of peroxide, or causes the division of olefin unit and/or ionization with ultraviolet ray, electron beam, gamma-radiation, high energy particle and produce).Polymer chain free radical and maleimide are by two key additions or free radical coupling Cheng Jian.Two such chains and same molecular reaction just form crosslinked.N, N '-1,3-phenylene maleimide are preferred examples.Peroxide initiator is a benzoyl peroxide, 1,1-two-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3.
The formation of the intensive internet of polymer chain needs a large amount of initators (if being lower than its solubility limit in polymer), and this may cause the primary radical termination in the polymer chain free radical of lazy flow.In addition, form the crosslinking agent of stablizing the chain free radical and can consume initator, do not form the required polymer chain free radical of dense network and do not produce.For making the adjacent polymer chains coupling, interactional free radical must have similar reactivity to the polymer chain free radical.Yet the more important thing is that the polymer chain free radical will reach finite concentration.Selected initator will split into the free radical of the high reaction activity with very high trigger rate under the temperature that relaxes.The necessary degree of cross linking in internet that forms the polymer chain of " densification " depends on many factors, as the type of initiator type, functional group, elementary radical reaction activity, efficiency of initiation, coupling agent or crosslinking agent, mechanism of crosslinking, with the distinctive interaction of polymer, the microstructure of polymer, the reactivity of free polymer readical, the flowability and the concentration of free radical, the control that it is subjected to temperature control to a great extent and/or is subjected to luminous intensity in light-initiated or optical sensibilization.
When using with the alkyl peroxide initator that has more activity, the organo-metallic crosslinker of enol salt also make good progress.More stable benzoyl and isobutyl peroxide free radical are tending towards lower crosslinked efficiency of initiation, if but the solubility of raising in polymer is to reach higher initiator concentration, and these initators also suit so.But the organometallic reagent (as diketone acid metal salt and derivative thereof) with chelated mineral of multiple stable oxidation states is promising, and acetopyruvic acid aluminium is a preferred example.If metal has redox active at the chelating state, they potentially the catalysis peroxide decomposition or as light activating agent or light trigger sensitizer.Useful peroxide initiator is a benzoyl peroxide, 1,1-two-(t-butylperoxy)-3,3,5-trimethyl-cyclohexane and 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3.They can be with other reagent glue chains or carry out crosslinked with heat, ultraviolet ray, visible light, electron beam, high energy particle (as alpha particle) bump, ionising radiation (as gamma-rays) and discharge (as plasma) separately.
But described additive comprise be not limited to listed these: initator: 1,1-two (t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3, tert-butyl peroxide, dicumyl peroxide, methyl-ethyl-ketone peroxide, m-chloro-benzoic acid peroxide, benzoyl peroxide.Crosslinking agent (comprising coupling agent): acetopyruvic acid aluminium, acetopyruvic acid cobalt (III), acetopyruvic acid cobalt (II), ketene acetal nickel, N, N '-1,3-phenylene maleimide, divinylsulfone, three propargyl benzene, divinylbenzene, VTES, HMDS (hexamethyldislazane), trimethylolpropane tris vinethene, trimethylolpropane, trimethyl acrylic ester, trihydroxy methyl-propane-allyl ether, cyanuric acid alkatriene propyl diester and triallyl phosphate.
Second method (being Type II) is that sulphonyl ammonia is crosslinked.Sulphonyl-imidazoles or equivalent form sulphonyl ammonia with being reflected at of aromatic amine and are connected between styrene units.Styrene sulfonic acid unit and 1,1 in the polymer chain '-reaction of carbonyl dimidazoles forms styrene sulphonyl imidazoles.Imidazole molecule is a good leaving group, even the nucleopilic reagent (as aromatic diamines) that relaxes also can be replaced them.Suitable aromatic diamines is the 4-dapsone.
The major advantage of two kinds of crosslinked schemes is that crosslinking agent can be added in the solution of polymer, can normally sneak into and casting mold.Then the HUX element heat in baking oven, in baking oven, heat or be exposed in the radioactive ray to remove residual solvent.It is one object of the present invention that additive is added prescription.
Fig. 2 is the part stereogram of exchange of moisture element (or ventilation equipment core) 20, and described exchange component comprises a composite membrane 10, contains first chamber 22 of first fluid, contains second chamber 24 of second fluid, many spacers (rib line) 16 that is adhered on the film 10.Element 20 comprises a series of first and second chambeies that replace.A capping 26 is used for the chamber of airtight most significant end and least significant end.
As shown in Figure 2, film 10 is stacked mutually to form ventilation equipment core 20.When putting in the ventilation equipment core for every layer, its direction is rotated 90 ℃.So just in the ventilation equipment core, form the heat of cross-current type and the exchange of water.What demonstration still not can be completely achieved is the adverse current arrangement of layer.Here each arranged not rotation along single direction layer in the ventilation equipment core.The manifold of a complexity is used for air-flow is introduced other each layers that layer is piled.These manifolds are placed the reverse side of ventilation equipment core.If necessary the one side of no manifold in the ventilation equipment core is sealed to external environment condition.
Spacer 16 as illustrated in fig. 1 and 2 is made of a series of rib line, generally it is adhered to and leads the wet polymer surface.These rib lines contain a kind of synthetic polymer composition, particularly polyvinyl chloride, and its cross section is rectangle or circle.(not shown) in other embodiment, spacer 16 can be corrugated cardboard or plastic sheet.In some embodiments, spacer 16 can be the pearl of a series of adhesives.Described adhesive can be a kind of hot melt, sloppy heat or solid adhesive, also can be thermoplasticity or thermosetting plastics.The HUX element can contain some to the effective specific sub-element of quality (for example moisture) interchanger.Basic sub-element is as follows: (a) the hydro carbons hydrophilic polymer membrane that water or other high polar liquid or gas are had the good penetration ability, (b) give the mechanically stable of film and during operation planarization support framework and (c) be used for the manifold of distribution fluid on the film surface.Disclosed HUX element is a global design, wherein is combined to whole three sub-elements in the complete component structure and is assembled into an integral body.Can be fixed on by simple accumulation with this element and make the equipment that possesses this structure in the shell.
Embodiment
The sensible heat and the latent heat exchanger of a cross-current type have been constructed.Strengthen the film of making interchanger on the body by one deck sulfonated phenylethylene-olefin polymer being laminated to the nylon nonwoven.Described film is stacked mutually, use a kind of polyvinyl chloride spacer that scribbles adhesive.The orientation of polyvinyl chloride spacer is 90 ° of angles in each adjacent laminates.Separately layer has an identical flow direction in exchanger core: 1,3,5,7 etc. have same stream to, 2,4,6,8 etc. have the flow direction that is 90 ° of angles in aforementioned direction.The edge of each layer seals with two-sided tape in the exchanger core.The cross-flow interchanger is placed test apparatus, wherein control flow velocity, the temperature and humidity of two strands of air-flows.One gas flow temperature is that 90  temperature and relative saturation humidity are 55%, and another burst gas flow temperature is that 70  and relative saturation humidity are 50%.The exchange of sensible heat and latent heat between the following two strands of air-flows of supervision different in flow rate.Data are shown in Fig. 3 with the form of curve.Shown air-flow is normalized to the function of square feet membrane area.This allows us to utilize the interchanger and the interchanger respect to one another of the more various materials of exchange area in the interchanger.Curve shows that the gross efficiency of such interchanger of use sulfonated phenylethylene-olefin polymer films reaches more than 70%.

Claims (20)

1, a kind of element that is used between the first fluid and second fluid, transmitting heat and moisture, described element comprises: a slice composite membrane at least, described composite membrane are arranged in first chamber of at least one first fluid that is used to flow through and at least one and are used to flow through between second chamber of second fluid; Wherein heat and moisture can transmit between the first fluid and second fluid via described composite membrane.
2, according to the element of claim 1, wherein said composite membrane comprises: a kind of partly sulfonated at least wet polymer of leading, this polymer comprise and derive from least a aryl vinyl residues of monomers; With an enhancing base material with described polymer phase bonding.
3, according to the element of claim 2, it also comprises the spacer at least one one side that is arranged in described composite membrane.
4, according to the element of claim 3, wherein said at least one spacer has certain thickness on the direction perpendicular to described composite membrane surface, and the height in described thickness and described first chamber is suitable.
5, according to the element of claim 3, flowing to of the first fluid in the y direction of wherein said at least one spacer and first chamber is parallel.
6, according to the element of claim 5, wherein the flow direction of the first fluid in first chamber is perpendicular to the flow direction of second fluid in second chamber.
7, according to the element of claim 5, wherein the flow direction of second fluid in the flow direction of the first fluid in first chamber and second chamber is opposite.
8, according to the element of claim 3, wherein at least one spacer contains many synthetic polymer rib lines.
9, according to the element of claim 3, wherein at least one spacer contains adhesive component.
10, according to the element of claim 3, wherein at least one spacer contains corrugated plating.
11, according to the element of claim 2, the wherein said composite membrane of a slice at least comprises the multi-disc composite membrane, and described at least one first chamber and described at least one second chamber comprise a plurality of first chambeies that replace and second chamber, isolates with composite membrane each other.
12, according to the element of claim 2, wherein said enhancing base material contains a kind of adhesive-bonded fabric.
13, according to the element of claim 2, wherein said enhancing base material contains a kind of microporous barrier.
14, according to the element of claim 2, wherein said enhancing base material contains at least a synthetic fibers.
15, according to the element of claim 14, wherein said at least a synthetic fibers comprise a kind of polyolefin at least.
16, according to the element of claim 2, the wherein said wet polymer of leading also contains a kind of additive, and described additive is selected from antioxidant, antimicrobial, fire retardant, UV stabilizer, hydrophilic plasticizer and their mixture.
17, according to the element of claim 2, the wherein said wet polymer of leading contains at least a antioxidant, at least a antimicrobial and at least a fire retardant.
18, according to the element of claim 2, the wherein said wet polymer of leading utilizes a kind of peroxide initiator and a kind of organic metal enolate coupling agent to carry out crosslinked.
19, according to the element of claim 18, wherein said peroxide initiator is 1,1-two-(t-butylperoxy)-3,3, and the 5-trimethyl-cyclohexane, described organic metal enolate coupling agent is an acetopyruvic acid aluminium.
20, according to the element of claim 18, wherein said peroxide initiator is 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3.
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JP2004535270A (en) 2004-11-25
WO2002072242A1 (en) 2002-09-19

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