United States Patent [191
`Bonaventura et al.
`
`[11] Patent Number:
`[45] Date of Patent:
`
`4,761,209
`* Aug. 2, 1988
`
`[54] SYSTEM FOR THE EXTRACTION AND
`UTILIZATION OF OXYGEN FROM FLUIDS
`[75] Inventors: Joseph Bonaventura; Celia
`Bonaventura, both of Beaufort, N .C.;
`Joseph C. Van Ryzin, Kailua, Hi.;
`Bruce D. Zenner, Beaufort, N.C.; C.
`William Anderson, Durham, NC.
`Aquanautics Corporation, San
`Francisco, Calif.
`The portion of the term of this patent
`subsequent to Jul. 29, 2003 has been
`disclairned.
`[21] Appl. No.: 855,706
`[22] Filed:
`Apr. 25, 1986
`
`[73] Assignee:
`
`[ * ] Notice:
`
`[62]
`
`Related US. Application Data
`Division of Ser. No. 653,850, Sep. 24, 1984, Pat. No.
`4,602,987.
`
`[51] Int. cm ............................ .. c2513 1/02
`[52] us. or. .................................. .. 204/129; 204/265;
`204/266; 204/DIG. 4; 429/ 12; 429/122; 123/2;
`123/22; l23/DIG. 13; 55/16; 55/158
`[58] Field of Search ............. .. 204/ 129, 265, 266, 263,
`204/DIG. 4, DIG. 6; 123/2, 22, DIG. 13;
`429/12, 122; 55/16, 158
`References Cited
`U.S. PATENT DOCUMENTS
`
`[56]
`
`4,251,452 2/ 1981 McAuliffe et al. ........... .. 260/429 R
`4,475,994 10/1984 Gagné et al. .... ..
`4,542,010 9/1985 Roman et al. ........................ .. 55/16
`
`OTHER PUBLICATIONS
`International Application No. PCT/US85/02l24; SRI
`
`International (Roberts et al.), ?led: Oct. 28, 1985 enti
`tled, “Gas Separation Process”.
`Primary Examiner-R. L. Andrews
`Attorney, Agent, or Firm—-Oblon, Fisher, Spivak,
`McClelland & Maier
`[57]
`ABSTRACT
`A method for extracting oxygen from a ?uid environ
`ment, which comprises the steps of (l) contacting a ?rst
`?uid environment containing oxygen with a ?rst sur
`face of a ?rst oxygen permeable membrane having a
`?rst and a second surface, wherein the membrane sepa~
`rates the environment from an interior space of a closed
`container, (2) transporting a carrier ?uid into contact
`with the second surface of the membrane, wherein the
`carrier ?uid is con?ned in the closed container and the
`carrier ?uid contains a binding-state oxygen carrier,
`whereby oxygen which diffuses through the membrane
`binds to the carrier to give a bound oxygen complex, (3)
`transporting the carrier ?uid containing the bound oxy
`gen complex to a ?rst electrode compartment of an
`electrochemical cell which forms a second portion of
`the closed container, (4) electrochemically modifying
`the binding-state oxygen carrier to an oxidation state
`having less binding af?nity for oxygen, thereby releas
`ing free oxygen into the carrier ?uid and producing a
`nonbinding-state oxygen carrier, (5) removing oxygen
`from the carrier ?uid, (6) transporting the carrier ?uid
`containing the nonbinding-state oxygen carrier to a
`second electrode compartment of
`an electrochemical
`cell which forms a third portion of the closed container,
`and (7) electrochemically modifying the nonbinding
`state oxygen carrier to the binding-state oxygen carrier,
`is disclosed along with an apparatus useful for carrying
`out the method of the invention.
`
`42 Claims, 15 Drawing Sheets
`
`02
`
`REDUCED STATE
`LOA DING
`OXYGEN CARRIER
`‘ STA TION
`
`sou/v0
`OXYGEN COMPLEX
`
`REDUCING
`STA no”
`
`l
`
`REDUCED STATE
`OXYGEN CA RRIER
`
`UNLOADING
`STATION
`
`l
`
`02
`
`OXID/ZING
`sm TION
`
`<
`OXIDIZED STATE OXYGEN
`CARRIER a FREE OXYGEN
`
`CO2 Solutions Inc.
`Exhibit 2001
`Akermin, Inc. v. CO2 Solutions Inc.
`IPR2015-00880
`Page 1 of 37
`
`

`

`US. Patent
`
`Aug. 2, 1988
`
`Sheet 1 0f 15
`
`4,761,209
`
`REDUCED STATE
`OXYGEN CARR/ER
`
`LOA DING
`STA TION
`
`BOUND
`OXYGEN COMPLEX
`
`REDUCING
`STA TION
`
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`
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`
`OX/D/ZED STATE OXYGEN
`CARRIER 8 FREE OXYGEN
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`
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`Page 2 of 37
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`

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`US. ‘Patent
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`Aug. 2, 1988
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`Page 3 of 37
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`

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`US. Patent Aug. 2, 1988
`
`Sheet 3 of 15
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`4.761,209
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`Page 4 of 37
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`

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`US. Patent Aug. 2, 1988
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`Sheet 4 of 15
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`Page 5 of 37
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`

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`Aug. 2, 1988
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`U.S. Patent
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`Aug. 2, 1988
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`US. Patent Aug. 2, 1988
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`US. Patent Aug. 2, 1988
`
`Sheet 8 of 15
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`4,761,209
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`~ENG/NE
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`Page 9 of 37
`
`

`

`US. Patent Aug. 2, 1988
`MEMBRANEL
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`Sheet 9 of 15
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`Page 10 of 37
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`

`

`US. Patent
`
`Aug. 2, 1988
`
`Sheet 10 of 15
`
`4,761,209
`
`HOLLOW F/BER CARTRIDGE
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`Page 11 of 37
`
`

`

`US. Patent Aug. 2, 1988
`
`Sheet 11 0f 15
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`4,761,209
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`Page 12 of 37
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`

`

`US. Patent Aug. 2, ‘1988
`
`Sheet 12 of 15
`
`4,761,209
`
`ABSORBANCE
`
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`
`FIG. 16
`
`Page 13 of 37
`
`

`

`US. Patent Aug. 2, 1988
`
`Sheet 13 0f 15
`
`4,761,209
`
`PICKET FENCE PORPH YR/N -
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`
`Page 14 of 37
`
`

`

`U.S. Patent
`
`Aug. 2, 1988
`
`Sheet 14 of 15
`
`4,761,209
`
`GLASS PLATES
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`Page '15 of 37
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`Page 15 of 37
`
`

`

`U.S. Patent
`
`Aug. 2, 1988
`
`Sheet 15 of 15
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`4,761,209
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`Page 16 of 37
`
`

`

`1
`
`4,761,209
`
`SYSTEM FOR THE EXTRACTION AND
`UTILIZATION OF OXYGEN FROM FLUIDS
`
`This is a division, of application Ser. No. 653,850,
`?led Sept. 24, 1984.
`
`2
`water in equilibrium with air. Practical methods have
`not yet been devised for extracting and utilizing this
`vast amount of oxygen for the maintenance of man in an
`undersea environment. Fish, however, have obviously
`solved the problem of oxygen extraction from seawater.
`Fish species weighing well over a thousand pounds and
`burning metabolities at rates roughly comparable to
`that of man easily extract adequate dissolved oxygen
`from seawater for their varied activities. Moreover,
`many species of ?sh transfer oxygen from seawater into
`a gaseous state. These ?sh, ones that possess swim blad
`ders, are able to pump and concentrate oxygen against
`enormous hydrostatic pressure gradients. In certain ?sh
`species oxygen is transported from the dissolved state in
`seawater, with a p02 of 0.2 atmospheres, to a gaseous
`phase in the swim bladder where the p02 may exceed
`100 atmospheres.
`Many attempts to develop methodologies of extract
`ing oxygen from gaseous mixtures or water are known.
`Warne et al, U.S. Pat. No. 2,217,850, and Folger et al,
`U.S. Pat No. 2,450,276, disclose processes of separating
`oxygen from other gases using solutions of cobalt com
`pounds. However, these techniques would be ineffec
`tive in a liquid system, e.g., seawater, since the com
`pounds are in solution and would be washed away if
`contacted with liquids rather than the disclosed gases.
`Miller, U.S. Pat. No. 3,230,045, discloses using oxygen
`binding chromoproteins such as hemoglobin and hemo
`cyanin to separate oxygen from other gases. The chro
`moproteins are kept moist or in solution and are immo'
`bilized on ?lter paper where they may be bound by a
`binder such as ?brin; an electrolyte such as sodium
`chloride may also be present. However, this technique
`would also be ineffective in a liquid system since the
`protein is not insoluble and thus would be washed away
`if water were allowed to ?ow through the system.
`Moreover, there is no provision for regeneration of
`oxidized (inactive) oxygen carriers that would be
`formed in this system. Bodell, U.S. Pat. No. 3,333,583,
`and Robb, U.S. Pat. No. 3,369,343, disclose apparatus
`for extracting oxygen from seawater using thin tubes of
`silicone rubber or a membrane of silicone rubber, re
`spectively. However, neither the capillary networks
`nor the permeable membranes working alone have been
`found to be practicable in real-life situations. Isomura,
`U.S. Pat. No. 3,377,777, discloses concentrating oxygen
`from natural waters by equilibration with exhaled gases,
`i.e., by utilizing large areas of gas-water interface and
`simple diffusional considerations such that the partial
`pressure of the gas phase and the partial pressure of the
`liquid phase in the extraction zone provide for release of
`oxygen from the liquid phase into the gas phase and
`absorption of CO2 by the water phase. Additionally, the
`solubility of oxygen in seawater is decreased by heating
`the seawater, and this heating also increases the solubil
`ity of CO2. However, the requirement of heating the
`seawater results in an energetically undesirable process.
`Rind, U.S. Pat. No. 4,020,833, discloses an oxygen
`source for closed environments comprising a mixture of
`a metallic superoxide, which releases oxygen upon
`contact with CO2 and water vapor, and a material
`which absorbs CO2. However, this system suffers from
`the defect of the capacity being limited by the bulk
`amount of mixture which can be carried, i.e., it is not
`capable of continuously producing oxygen without
`replenishment. Iles et al, U.S. Pat. No. 4,165,972, dis
`closes separating oxygen from gas mixtures using metal
`
`20
`
`25
`
`30
`
`35
`
`BACKGROUND OF THE INVENTION
`1. Field of the Invention
`This invention relates to an apparatus for and a pro
`cess of extracting oxygen from ?uids in which oxygen is
`dissolved.
`2. Description of the Prior Art
`Oxygen is required in many important chemical reac
`tions utilized by humans, the most important being life
`supporting respiration. When these reactions are carried
`out on the surface of the earth, the oxygen content of air
`is often suf?cient to provide enough oxygen for the
`desired reaction. However, there are many instances
`when oxygen is required at concentrations higher than
`those normally present in air. For example, pure oxygen
`is required in large quantities by the steel industry. Oxy
`gen is used to volatilize carbon and other nonmetal
`impurities with greater speed and control than would be
`possible if air alone were used.
`Persons having lung
`disorders which interfere with their ability to obtain
`oxygen from air likewise require puri?ed oxygen for
`home or hospital use. Miners working in so-called bad
`air, i.e., air of less than normal oxygen content, require
`bottled oxygen at present. Oxygen has proven highly
`efficient for the treatment of liquid effluents in sewage.
`Incineration of wastes in closed systems using pure
`oxygen has become an important method for disposing
`of toxic wastes.
`Although various preparative methods exist for pro
`ducing oxygen on a small scale, oxygen is generally
`prepared by the fractional distillation of liquid air when
`it is required in large quantities. Typically, ?ltered air is
`passed through an alkali absorbant in order to remove
`moisture and carbon dioxide. The air is then com
`pressed, and the heat of compression is removed by
`ordinary‘ cooling procedures. The cooled and com
`pressed air is then allowed to expand, taking advantage
`of the fact that a compressed gas cools as it expands.
`The compressed gas is then recompressed, cooled, and
`expanded again multiple times in order to ?nally pro
`duce liqui?ed air. The liquid air is allowed to warm in
`order to boil off nitrogen and other light impurities,
`leaving liquid oxygen. The liquid oxygen may be stored
`in that form or as compressed gaseous oxygen.
`Although this process produces oxygen in a commer
`cially useful form, it is a process which requires a large
`immovable plant and a delivery system for transporting
`either cryogenic liquid oxygen or compressed gas.
`While the oxygen distribution system has worked well
`for the steel industry, there are many applications
`where local production of oxygen would be useful. For
`example, home or hospital generators of oxygen would
`be extremely useful for persons afflicted with breathing
`disorders. Even large consumers of oxygen, such as the
`steel industry, would bene?t by a process which re
`duces the energy requirements of producing oxygen
`from air by liqui?cation.
`Furthermore, one of the primary problems which
`hinders man in his efforts to explore and develop the
`ocean realms is the lack of a ready supply of oxygen. In
`most of the world’s oceans, the oxygen content of both
`shallow and deep waters is similar to that of surface
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Page 17 of 37
`
`

`

`5
`
`10
`
`20
`
`30
`
`15
`
`4,761,209
`3
`4
`Spectrometry of Macroporous Hemoglobin Particles”,
`chelates as sorbents. However, the technique is not
`J. Opt. Soc. Am., 70, 560-562 (1980), discloses glutaral
`extendable to the extraction of oxygen from water.
`Many compounds in solution have been examined
`dehyde cross-linked hemoglobin and its functional
`with respect to their oxygen absorption properties and
`properties. The preparation is described as being made
`the mechanistics thereof. The properties of hemoglo
`up of macroporous particles. Hallaway et al, “Changes
`bins, hemerythrins and hemocyanins, the naturally oc
`in Conformation and Function of Hemoglobin and
`curring oxygen carriers, have been the subject of nu
`Myoglobin Induced by Adsorption to Silica”, BBRC,
`86, 689-696 (1979), discloses that hemoglobin adsorbed
`merous studies, as
`documented in Bonaventura et al, J.
`Am. Zool., 20, 7 (1980) and 20, 131 (1980). Arti?cial
`on silica is somewhat different from hemoglobin in
`oxygen carriers and their properties in solution are
`solution. The adsorbed form is not suitable for 02 extrac
`described by a number of researchers. Traylor et al,
`tion from liquids. Antonini et al, “Immobilized Hemo
`proteins”, Methods of Enzymology, 44, 538-546 (1976),
`“Solvent Effects on Reversible Formation and Oxida
`tive Stability of Heme-Oxygen Complexes”, J.A.C.S.
`discloses standard immobilization techniques as applied
`96, 5597 (1974) discloses the effect of solvent polarity
`to hemoglobin and their functional consequences. Men
`on oxygenation of several heme-base complexes pre
`tion is made of hemoproteins bound to cross-linked
`pared by reduction with sodium dithionite or a mixture
`insoluble polysaccharides such as Sephadex or Se
`of Pd black and calcium hydride. Crumbliss et al, “Mo
`pharose, using a pre-activation of the resin with CNBr.
`nomeric Cobalt-Oxygen Complexes”, Science, 6, June
`Rossi-Fanelli et al, “Properties of Human Hemoglobin
`1969, Volume 164, pp. 1168-1170, discloses Schiff base
`Immobilized on Sepharose 4B”, Eur. J. Biochemistry,
`complexes of Co(II) which form stable cobalt-oxygen
`92, 253-259 (1978), discloses that the ability of the he
`species in solution instead of cobalt-oxygen-cobalt
`moglobin to be bound to Sepharose 4B is dependent
`bridged complexes. Crumbless et al, “Monomeric Oxy
`upon the conformational state of the protein. Colosimo
`gen
`Adducts
`of
`N,N’-Ethylenebis
`et al, “The Ethylisocyanate (EIC) Equilibrium of Ma
`(acetylacetoniminato) ligandcobalt(III): Preparation
`trix-Bound Hemoglobin”, BBA, 328, 74-80 (1973), dis
`and Properties”, J.A.C.S. 92, 55 (1970), discloses a se
`closes Sephadex G-lOO, Sephadex DEAE-ASO and Se
`25
`ries of monomeric molecular oxygen carriers based on
`phadex CM-C50 as supports for human hemoglobin
`cobalt ligand complexes. Dufour et al, “Reaction of
`insolubilization. The paper shows that the affinity of the
`Indoles with Molecular Oxygen Catalyzed by Metallo
`insolubilized protein for BIC is increased relative to that
`porphyrins”, Journal of Molecular Catalysis, l, 277
`in solution. Lampe et al, “Die Bindung von Sauerstoff
`(1980), discloses the catalysis of the oxygenation of
`an trager?xiertes Hamoglobin”, Acta Biol. Med.
`simple, alkylsubstituted indoles by Co(II), Co(III), and
`Germ, 33, K49-K54 (1974), discloses studies on CM
`Mn(III) meso-tetraphenyl-porphines wherein a ternary
`Sephadex insolubilized hemoglobins. Lampe et al, “Der
`complex oz-CoTPP-indole is formed initially. Brault et
`Ein?uB der Immobilisierung von Hamoglobin auf
`al, “Ferrous Porphyrins in Organic Solvents: I. Prepa
`dessen Sauerstof?ndung”, Acta Biol. Med. Germ, 34,
`ration and Coordinating Properties”, Biochemistry, 13,
`359-363 (1975), discloses studies on CM-Sephadex in
`35
`4591 (1974), discloses the preparation and properties of
`solubilized hemoglobins. Pommerening et al, “Studies
`ferrous deutereporphyrin dimethyl ester and ferrous
`on the Characterization of Matrix-Bound Solubilized
`mesotetraphenylporphine in various organic solvents.
`Human Hemoglobin”, Internationales Symposium uber
`Chang et al, “Kinetics of Reversible Oxygenation of
`Struktur und Funktion der Erythrezyten (Rapoport and
`Pyrroheme-N-[3-(l-imidazolyl)propyl]amide”,
`dis
`Jung, ed.), Berlin Akademie-Verlag Press, 179-186
`40
`closes studies on the oxygenation of pyrroheme-N-[3
`(1975), discloses Sepharose-Sephadex types of insolubi
`(l-imidazolyl)propyl]amide, i.e., a synthesized section
`lization. Brunori et al, “Properties of Trout Hemoglobin
`of the myoglobin active site. Castro, “Hexa and Pen
`Covalently Bound to a Solid Matrix”, BBA, 494(2),
`tacoordinate Iron Poryhyrins”, Bioinorganic Chemis
`426-432, discloses Sepharose 4B or Sephadex G-200,
`try, 4, 45-65 (1974), discloses the direct synthesis of
`activated by CNBr, to immobilize the hemoglobin.
`45
`hexa and pentacoordinate iron porphyrins, i.e., the pros
`Some changes in the functional properties of the hemo
`thetic groups for the active sites of certain cytochrome
`globin were found.
`and globin heme proteins. Chang et al, “Solution Be
`Various techniques for the insolubilization (or immo
`havior of a Synthetic Myoglobin Active Site”, J .A.C.S.,
`bilization) of biological materials have been developed,
`95, 5810 (1973), discloses studies on a synthesized sec
`though not described in conjunction with insolubiliza
`tion of the myoglobin active site and indicates that the
`tion and utilization of oxygen carriers. Stanley, U.S.
`oxygen binding reaction does not require the protein
`Pat. No. 3,672,955, discloses a technique for the prepa
`Naturally occurring oxygen carriers have been chemi
`ration of an insoluble, active enzyme, a biological cata
`cally cross-linked and their properties described.
`lyst, wherein an aqueous dispersion of the enzyme is
`Bonsen et al, U.S. Pat No. 4,053,590, discloses a
`poly
`emulsi?ed with an organic polyisocyanate, mixed with
`merized, cross-linked, stromal-free, hemoglobin pro
`a solid carrier and the volatile components are then
`posed to be useful as a blood substitute. Morris et al,
`evaporated from the mixture. Wood et al, U.S. Pat. No.
`U.S. Pat No. 4,061,736, discloses intramolecularly
`3,928,138, discloses a method of preparing a bound
`cross-linked, stromal-free hemoglobin. Wong, U.S. Pat.
`enzyme wherein, prior to foaming, an isocyanate
`No. 4,064,118, discloses a blood substitute or extender
`capped polyurethane is contacted with an aqueous dis
`prepared by coupling hemoglobin with a polysaccha
`person of enzyme under foam-forming conditions,
`whereby polyurethane foams containing integrally
`ride material. Mazur, U.S. Pat. No. 3,925,344, discloses
`a plasma protein substitute, i.e., an intramolecular,
`bound enzyme are obtained. Unsworth et al, U.S. Pat.
`cross-linked hemoglobin composition.
`No. 3,928,230, discloses the encapsulation of ?uids and
`Numerous papers have been published on immobili
`solids by dissolving a water-insoluble polymerizable
`zation of hemoglobin and its functional consequences,
`epoxy monomer in a solvent having high af?nity for
`but not in connection with processes for efficient oxy
`water; dispersing the monomer solution in water; dis
`gen extraction from ?uids. Vejux et al, “Photoacoustic
`persing in the so-formed aqueous dispersion the sub
`
`55
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`
`65
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`

`4,761,209
`5
`stance to be encapsulated; adding a polymerizing agent
`in a solvent having a higher af?nity for water than for
`the polymerizing agent; and polymerizing until poly
`merization of the monomer is complete. Wood et al,
`U.S. Pat. No. 3,929,574, discloses an enzyme integrally
`bound to a foamed polyurethane prepared by, prior to
`foaming, contacting an isocyanate-capped polyurethane
`with an aqueous dispersion of enzyme under foam
`forming conditions, whereby polyurethane foams con
`taining integrally bound enzyme are obtained. Hartde
`gen et a1, U.S. Pat. No. 4,094,744, discloses water-dis
`persible
`protein/polyurethane reaction products
`formed by admixing a water-dispersible, biologically
`active protein and'an isocyanate-capped liquid polyure
`thane prepolymer having a linear polyester backbone
`under essentially anhydrous conditions to form a solu
`tion, said protein and prepolymer reacting to form a
`watersoluble reaction product wherein the protein and
`prepolymer are bound together. Hartdegen et al, U.S.
`Pat. No. 4,098,645, discloses enzymes immobilized by
`the process of mixing the protein and an isocyanate
`capped liquid polyurethane prepolymer in the absence
`of water; foaming the mixture by reacting it with water
`to form a polyurethane foam. Huper et al, U.S. Pat. No.
`4,044,196, discloses proteins insolubilized using poly
`mers containing maleic anhydride or di- and polymeth
`acrylates. Huper et a1, U.S. Pat. No. 3,871,964, discloses
`proteins insolubilized using polymers containing anhy
`dride, di-methacrylate and a hydrophilic monomer.
`Many of the prior art problems were overcome by
`the invention disclosed in U.S. Pat. No. 4,427,416 and
`4,343,715, which disclose oxygen carriers which have
`been insolubilized at high concentrations by being en
`trapped and/or covalently linked to a polyurethane
`matrix or to comparable supports in states that are capa
`ble of reversible oxygen bonding and are regenerable in
`the event of oxidation. The material disclosed in these
`patents is generally known by the name “Hemos
`ponge”, since it is generally, though not necessarily,
`based on hemoglobin. The method and material as de
`scribed in these patents are perfectly capable of extract
`ing oxygen from various ?uid environments in useful
`form, but the rate of extraction is less than that which
`may be desired for many applications which involve a
`high rate of oxygen use. Accordingly, there remains a
`need for an improved apparatus and method for the
`extraction and utilization of oxygen from ?uids.
`
`6
`?uid is con?ned in said closed container and said carrier
`?uid contains a binding-state oxygen carrier, whereby
`oxygen which diffuses through said membrane binds to
`said carrier to give a bound oxygen complex, (3) trans
`porting said carrier fluid containing said bound oxygen
`complex to a ?rst electrode compartment of an electro
`chemical cell which forms a second portion of said
`closed container, (4) electrochemically modifying said
`binding-state oxygen carrier to an oxidation state hav
`ing less binding af?nity for oxygen, thereby releasing
`free oxygen into said carrier and producing a nonbind
`ing-state oxygen carrier, (5) removing oxygen from said
`carrier ?uid to give an oxygen-depleted carrier ?uid, (6)
`transporting said oxygen-depleted carrier ?uid contain
`ing said nonbinding-zstate oxygen carrier to a second
`electrode compartment of an electrochemical cell
`which forms a third portion of said closed container,
`and (7) electrochemically modifying said nonbinding
`state oxygen carrier to said binding-state oxygen car
`rier. The invention may also be practiced more broadly
`without carrying out the oxidation and reduction steps
`by replacing steps (3)-(7) with the following steps: (3)
`transporting said carrier ?uid containing said bound
`oxygen complex to a second portion of said closed
`container, (4) removing oxygen from said carrier ?uid
`to give an oxygen-depleted carrier ?uid, and (5) trans
`porting said oxygen-depleted carrier ?uid into contact
`with said second surface of said membrane. The present
`invention also comprises an apparatus by which this
`method can be carried out, which brie?y comprises a
`container having a gas permeable membrane which at
`least in part de?nes an inner space of said container, a
`carrier ?uid as described above in contact with the
`inner surface of the membrane and means for removing
`oxygen from the carrier ?uid so that the oxygen can be
`utilized for its desired purpose.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`A more complete appreciation of the invention and
`many of the attendant advantages thereof will be
`readily obtained as the same becomes better understood
`by reference to the following detailed description when
`considered in connection with the accompanying draw
`ings, wherein:
`FIG. 1 is a schematic diagram of a generalized pro
`cess of the invention.
`FIG. 2 is a schematic diagram of an embodiment of an
`oxygen extraction apparatus showing the operation of
`an electrochemical oxygen unloading system.
`FIG. 3 is a schematic diagram of a preferred embodi
`ment of the invention in which extracted oxygen is
`consumed in a fuel cell.
`FIG. 4 is a schematic diagram of a preferred embodi
`ment of the invention in which extracted oxygen is
`released in gaseous form through an oxygen permeable
`membrane.
`FIG. 5 is a schematic diagram of a generalized pro
`cess for removing carbon dioxide formed as a by
`product in the consumption of the oxygen produced by
`the process of the invention.
`FIG. 6 is a schematic diagram of an apparatus for
`removing carbon dioxide which utilizes enzyme immo
`bilized in one compartment of a two-compartment
`chamber divided by a membrane.
`FIG. 7 shows an embodiment for removing carbon
`dioxide by the countercurrent ?ow of water and a gas
`stream containing carbon dioxide.
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`SUMMARY OF THE INVENTION
`Accordingly, one object of the invention is to pro
`vide an apparatus capable of extracting oxygen from a
`?uid at a rate higher than that which has been previ
`ously available.
`It is a. further object of the invention to provide a
`system using an oxygen carrier that can be circulated
`between oxygen loading and unloading stations in order
`to simplify the cyclic nature of the oxygen loading and
`unloading processes.
`These and other objects of the invention as will here
`inafter become more readily apparent can be attained by
`providing a method for extracting oxygen from a ?uid
`environment, which comprises the steps of (1) contact
`ing a ?rst fluid environment containing oxygen with a
`?rst surface of an oxygen permeable membrane having
`a first and a second surface, wherein said
`membrane
`separates said environment from an interior space of a
`closed container, (2) contacting a carrier ?uid with said
`second surface of said membrane, wherein said carrier
`
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`4,761,209
`7
`FIG. 8 is a schematic diagram of a device for remov
`ing carbon dioxide from a gas stream based on a hollow
`?ber cartridge.
`FIG. 9 is a plot showing weight advantages for the
`system of the invention over other systems of providing
`stored oxygen in underwater applications.
`FIG. 10 is a plot showing weight advantages of un
`derwater propulsion systems using oxygen extracted
`according to the process of the invention over battery
`powered underwater propulsion systems.
`FIG. 11 shows an underwater vehicle which extracts
`oxygen by the process of the invention.
`FIG. 12 shows a block diagram of a spark or diesel
`engine operating in closed exhaust mode in combination
`with an oxygen extractor of the invention.
`FIG. 13 shows in block diagram form an oxygen
`extraction system of the invention.
`FIG. 14 shows in block diagram form speci?c param
`eters of a preferred embodiment of an oxygen extraction
`apparatus.
`FIG. 15 shows in graphical form cyclic voltammetry
`of an oxygen carrier of the invention.
`FIG. 16 shows in graphical form spectra of the oxi
`dized and reduced forms of an oxygen carrier of the
`invention.
`
`20
`
`15
`
`25
`
`8
`af?nities for oxygen of various oxygen carriers that
`exhibit at least two oxidation states. The basic charac
`teristics of a carrier that can be used in these preferred
`aspects of the invention are the existence of two oxida
`tion states for the carrier, the ability of the carrier to be
`cycled between the two oxidation states by an electro
`chemical reaction, and different binding af?nities for
`oxygen for the two oxidation states. Although the two
`oxidation states are referred to in this speci?cation as a
`“binding-state”and a “nonbinding-state”, these terms
`are relative rather than absolute. For example, if a non
`binding-state oxygen carrier has 70% of the binding
`capacity of the binding-state oxygen carrier, 30% of
`bound oxygen will be released by electrochemical cy
`cling if the binding-state oxygen carrier is saturated
`with oxygen. Naturally, more oxygen will be released if
`there is a greater difference in oxygen af?nity. Carriers
`having a binding capacity in the binding state at least
`twice that of the oxygen binding capacity of the non
`binding state are preferred. A binding/ nonbinding ratio
`of oxygen binding capacities of 10 or more is most pre
`ferred.
`The absolute binding af?nity of the oxygen carri