United States Patent
`Bonaventura et al.
`
`[11] Patent Number:
`.[45] Date of Patent:
`
`4,602,987
`Jul. 29, 1986
`
`SYSTEM FOR THE EXTRACTION AND
`UTILIZATION OF OXYGEN FROM FLUIDS
`[75] Inventors: Joseph Bonaventara; Celia
`Bonaventura, both of Beaufort, N.C.;
`Joseph C. Van Ryzin, Kailua, Hi.;
`Bruce D. Zenner, Beaufort; C.
`William Anderson, Durham, both of
`
`Wilson et al., A Synthetic Copper(I) Oxygen-Carrier as
`a Hemocyanin Model Compound 7/80.
`Wong et al., Oxidation Recution Reactions of Com-
`plexes with Macrocyelic Ligands, Oxygen Uptake Ki-
`netics, Equilibria, and Intermediate in Aqueous
`CO1 l(N4) Systems, J. Amer. Chem. Soc. 1980, vol. 102,
`No. 17.
`
`(List continued on next page.)
`
`[73] Assignee: Aquanautics Corporation, San
`Francisco, Calif.
`
`[21] Appl. No.: 653,850
`
`[22] Filed:
`
`Sep. 24, 1984
`
`Int. C1.4 ........................................... ~ .... C25B 1/02
`[51]
`[52] U.S. CI ..................................... 204/129; 204/!30;
`261/DIG. 28; 422/48; 423/129; 423/579
`[58] Field of Search .................... 204/130, 129; 55/16;
`422/48; 423/579, 129; 261/DIG. 28, 101
`
`[56]
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`4,008,047 2/1977
`4,011,306 3/1977
`4,198,792 4/I980
`4,287,170 9/1981
`4,422,936 12/1983
`4,442,297 4/1984
`4,444,662 4/1984
`4,475,994 !0/1984
`4,514,522 4/1985
`4,542,010 9/1985
`
`Petersen ................................ 422/48
`Fox, Jr~ ............................... 423/579
`Christensen et al ................ 423/579
`Erickson ............................. 423/579
`Riede et al ............................ 422/48
`HilI et al ............................. 549/200
`Conover ............................... 422/48
`Gagne et al ......................... 204/129
`Sievers et al ......................... 521/53
`Roman et al ........................ 423/579
`
`OTHER PUBLICATIONS
`
`U.S. Bureau of Mines Information, Circular No. 7906,
`1959, Stewart et al., Investigation of Oxygen Produc-
`tion by Metal Chelates.
`Industrial and Engineering Chemistry, vol. 39, No. 1,
`10/1947.
`Fogler, Regenerative Unit for Generating Oxygen
`Compressed Air Magazine, Nitrogen, Jul. 1985.
`Chemtech, 9/76, Aircraft Systems based on Metal Che-
`lates.
`Puxeddu et al., Equilibrium and Kinetic Parameters of
`the Oxygenation Reaction of Oxygen Carriers, Confor-
`mational ... Electrochemistry 198I.
`
`Primary Exarniner--K. L. Andrews
`Attorney, Agent, or Firm--Oblon, Fisher, Spivak,
`McCtelland & Maier
`
`[57]
`
`ABSTRAC~
`
`A method for extracting oxygen from a fluid en,¢iron-
`ment, which comprises the steps of(l) contacting a first
`fluid environment containing oxygen with a first sur-
`face of a first oxygen permeable membrane having a
`first and a second surface, wherein the membrane sepa-
`rates the environment from an interior space of a closed
`container, (2) transporting a carrier fluid into contact
`with the second surface of the membrane, wherein the
`carrier fluid is confined in the closed container and the
`carrier fluid contains a binding-state oxygen carrier,
`whereby oxygen which diffuses through the membrane
`binds to the cartier to give a bound oxygen complex, (3)
`transporting the carrier fluid containing the bound oxy-
`gen complex to a first 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 tess binding affirtity for oxygen, thereby releas-
`ing free oxygen into the carrier fluid and producing a
`nonbinding-state oxygen carder, (5) removing .oxygen
`from the carrier fluid, (6) transporting the carrier fluid
`containing the nonbinding-state oxygen carrier to a
`second electrode compartment of an electrochemical
`celt 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.
`
`20 Claims, 19 Drawing Figures
`
`REDUCED STATE
`
`BOUND
`OXYGEN COMPLEX
`
`LOADING
`STATION
`
`OXiGEN CARRIER=
`REDUCING
`STA T/ON
`
`! REDUCEO STATE
`
`OXYGEN CARRIER
`
`OXIDIZING
`STATION
`
`UNLOADING
`STATION I-OXIDIZED STATE OXYGEN
`I CARRIER 8 FREE OXYGEN
`
`Akermin, Inc.
`Exhibit 1004
`Page 1
`
`

`

`4,602,987
`
`Page 2
`
`OTHER PUBLICATIONS
`Harris et al., Electrochemical Investigation of a Series
`of Peroxo-Bridged Binoclear Cobalt Complexes, Inorg.
`Chem., 1980, 19, pp. 21-26.
`McLendon et al., Macrocycle-Promoted Oxygenation
`Reactions: 6/81.
`Equatorial and Axial Ligand Effects, Inorg. Chem. vol.
`
`t7, #2, 1978.
`Maeor et al., Oxidative Electrochemistry of Elec-
`tropolymerized Metaltoprotoporphyrin FiIms, Prince-
`ton Univ. 1983.
`Jones et al., Rodox Chemistry of Iron Tetraphenytpor-
`phyrin, Imidazolate-Chelated Protoheme, and
`Tholate-Chelated Protoheme.
`
`Akermin, Inc.
`Exhibit 1004
`Page 2
`
`

`

`U.S. Patent Jul. 29, 1986 Sheet 1 of 15 4,602,987
`
`REOUCED STATE
`OXYGEN CARRIER
`
`LOADING
`S TA TION
`
`BOUND
`OXYGEN CONIPLEX
`
`REDUCING
`STATION
`
`OXIDIZING
`STATION
`
`UNLOADING
`STATION
`
`L f
`
`REDUCED STATE
`OXYGEN CARRIER
`
`Akermin, Inc.
`Exhibit 1004
`Page 3
`
`

`

`U.S. Patent Jul. 29, 1986
`
`Sheet 2 of 15
`
`4,602,987
`
`ELECTRODE
`
`HYOROGEN
`ELECTROOE
`
`ELECTROLYTE
`
`Ib
`
`LOAO
`
`STATION
`
`FUEL CELL
`
`FLUID + C02
`
`IMMOBILIZED
`ENZYME
`
`FLUID
`
`FI6.5
`
`AQUEOUS
`BICARBONATE
`SOLUTION
`
`Akermin, Inc.
`Exhibit 1004
`Page 4
`
`

`

`U.S. Patent Jut 29, 1986
`
`Sheet 3 of 15 4,602,987
`
`END PLATE
`PLENUM (4) SEA WATER (2)
`
`Oz PICKUP
`CARTRIDGES
`
`O.B.C. ~
`CARRIER
`PUMP
`
`I0
`
`HIGH O2 CONTENT
`CARRIER STREAM
`
`} ELECTROCHEMICAL
`
`REACTOR 12
`
`~’~O~GAS
`COLLECTOR
`
`FIG. #
`02 EXTRACTION FLUID SYSTEM
`
`Akermin, Inc.
`Exhibit 1004
`Page 5
`
`

`

`U.S. Patent Jut. 29, 1986
`
`Sheet 4 of 15 4,602,987
`
`FLUID + C02
`
`FLUID
`
`Fi6.7
`
`.26c
`
`FLUID
`
`HZCO3(AQ)
`
`Akermin, Inc.
`Exhibit 1004
`Page 6
`
`

`

`OXYGEN SOURCES - IOKW FUEL CELL
`
`#500PS!
`DEPTH 5000m
`
`CRYOGENIC OXYGEN.y/
`DEPTH = 5000m
`"/ CRYOGENIC OXYGEN
`DEPTH = lO00m
`
`/
`
`/
`
`..,.,,,,,,"
`
`....’"’""" o ,~ CRYOGENIC OXYGEN
`DEPTH : IOOm
`
`OXYGEN HEME SYSTEM
`
`m)>
`
`FIG.9
`
`I
`
`I I P
`,t0 50 60
`~0
`MISSION TIME~ HR.
`
`I
`70
`
`I
`80
`
`I
`90
`
`

`

`SYSTEM OPTIMIZATION
`
`GASOLINE SPARK IGNITION ENGINE
`
`---" "-" H2- CRYO ACID FUEL CELL W/HEME
`
`....... tt2 -METHANOL ACID FUEL CELL
`
`/_.~.__~ ~"
`
`~ .~.~"
`
`FI6. fO
`
`2
`
`0.0
`
`¯
`
`i
`l.o ~ I
`I
`! DAY
`
`I
`13.o
`
`2.0 i
`LOG TIME,, HR.
`t WEEK I MONTH
`
`I
`4.0
`
`f YEAR
`
`m~>
`
`

`

`GEAR-DRiVEN ~
`
`~
`
`) T~RUSTERS
`
`20cm
`TO
`30cm
`
`HOLLOW TUBES
`FIG. lIB
`
`GILL SECTION MODULE
`/
`
`HEADERS PRO-
`TECtiVE SCREEN
`
`GILL
`
`HEME
`PUMP
`
`LIOUID
`
`tOKW.ENGINE
`
`50cm/sec.
`
`TUBES." VOLUME DENSITY 6.5 %
`TOTAL AREA 300m2- 450m2
`
`m)>
`
`FIG. I 1A
`
`

`

`U.S. Patent Jul. 29, 1986
`
`Sheet 8 of 15 4,602,987
`
`ENGINE
`
`(SPARK OR DIESEL)
`
`LOAD
`
`FUEL
`
`GAS
`
`EXHAUST
`GAS
`
`C02
`ABSORPTION
`CONTROLLER
`
`OXYGEN
`METERING DEVICE
`
`EXHAUST
`GAS
`COOLER
`
`OXYGEN
`MIXER
`
`CONDENSED
`WATER
`
`OXYGEN
`STORAGE
`
`02
`
`OXYGEN
`EXTRACTOR
`
`~ -~ ENVIRON-
`~ __ WATER
`
`MENTAL
`
`Akermin, Inc.
`Exhibit 1004
`Page 10
`
`

`

`U.S. Patent Jul. 29, 1986
`
`Sheet 9 of 15 4,602,987
`
`SEA WATER AT
`5mill 02
`400I!min.
`
`MEMBRANE~
`
`--JI IL-’I I~-~1 IL--
`
`HEME FLUID LOOP
`
`SEAWATER AT
`2.5ml/I 02
`4001/rain.
`
`7 0 ml/l OR
`Z _ VERY LOW
`
`PUMP
`
`MOTOR
`
`IATM PRESSURE VESSEL
`
`GASEOUS 02
`
`I
`
`< VALVES
`
`600mill
`k ATTACHED
`
`I
`
`! i/rain. 02
`
`FUEL
`TANK
`
`I
`i I
`
`I HEAT?
`
`NET POWER-- GROSS -
`HEME PUMP- CO2 SYS.
`
`EXHAUST
`
`l
`
`TRAP
`
`IH20
`
`.
`
`ANHYDRASE
`OR
`OTHER _
`I CARBOmC ACre
`I
`I
`
`?
`
`1 HEAT TO
`I ~ss4wA~R
`
`I
`
`Akermin, Inc.
`Exhibit 1004
`Page 11
`
`

`

`U.S. Patent jul.29,1986
`
`SheetlOofl5 4,602,987
`
`HOLLOW FIBER CARTRIDGE
`3"DIA. x 4S"LENGTH /
`
`WATER
`INLET
`
`WATER FLOW
`25 GAL./MIN.
`AT 20PSI
`
`~FI~O HOLLOW
`BERS
`
`SILICON RUBBER SKIN INSIDE POROUS2
`POLYSULFONE. SURFACE AREA 2.5m
`VEL: 647ml
`
`WATER
`OUTLET
`
`I G EAR PUMP
`
`CA RRIER FLOW
`0.25GAL./MtN.
`
`ELECTROCHEMICAL CELL
`8cm x 8cm x 62.5cm (LENGTH)
`20A AT O.tV
`
`!1
`
`SUPPLY
`
`HOLLOW FIBER CARTRIDGE
`
`f" DIA: x #S"LENGTH
`SURFACE AREA 0o25m2
`
`POLYVINYL CHLORIDE PIPING),
`
`FI G.
`
`SPATTERED GOLD
`SURFA CEO PLATES
`
`Akermin, Inc.
`Exhibit 1004
`Page 12
`
`

`

`T
`50#A
`
`HEMIN -’~ HEME
`REDUCTION
`
`-l.O00V
`
`BACKGROUND
`
`HEME --,- HEI~I N
`OXIDATION
`
`FIG.
`
`m)>
`
`

`

`U.S. Patent jul. 29, 1986
`
`Sheet 12 of 15 4,602,987
`
`2
`
`2
`
`I
`60Ohm
`
`I
`40Ohm
`
`FI6. 16
`
`Akermin, Inc.
`Exhibit 1004
`Page 14
`
`

`

`U.S. Patent
`
`Jut. 29, 1986
`
`Sheet 13 of 15 4,602,987
`
`’,co
`
`PICKET FENCE PORPHYRIN
`FI 6. ! 7A SHOV~v wn. rRO;V ~N CENTER
`
`CO- 0
`
`,CO F |
`.o \
`
`II I -’o
`
`({.]r,~,-,o CAPPED POR~~’~~PHYRlN
`~ t’l~. ll~ WiTH IRONIN CENTER
`
`Akermin, Inc.
`Exhibit 1004
`Page 15
`
`

`

`U.S. Patent JuL zg, 1986
`
`Sheet 14 of 15 4,602,987
`
`SPA
`
`GLASS PLATES
`
`CONTAINING
`CARRIER ELECTRODE
`
`TROUGH iN
`CELL CUP
`
`Akermin, Inc.
`Exhibit 1004
`Page 16
`
`

`

`ELECTRODE MESH
`
`BUBBLES TRAPPED iN MESH,
`
`rn~>
`
`~#~=~1~, 19 BUBBLES PRODUCED BY OXIDIZING THE CARR/ER SYSTEM. Fe (CAPPED) PORPHYRIN
`IN DMSO/ I - Me - IMIDAZOLE
`
`

`

`4,602,987
`
`2
`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
`5 that of man easily extract adequate dissolved oxygen
`from seawater for their varied activities. Moreover,
`many species of fish transfer oxygen from seawater into
`a gaseous state. These fish, ones that possess swim blad-
`ders, are able to pump and concentrate oxygen against
`10 enormous hydrostatic pressure gradients. In certain fish
`species oxygen is transported from the dissolved state in
`seawater, with a 002 of 0.2 atmospheres, to a gaseous
`phase in the swim bladder where the pO2 may exceed
`100 atmospheres.
`15 Many attempts to develop methodologies of extract-
`
`SYSTEM FOR THE EXTRACTION AND
`UTILIZATION OF OXYGEN FROM FLUIDS
`
`BACKGROUND OF THE INVENTION
`
`1. Field of the Invention
`This invention relates to an apparatus for and a pro-
`cess of extracting oxygen from fluids 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 sufficient 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 tung
`disorders which interfere with their ability to obtain
`oxygen from air likewise require purified 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, filtered air is
`passed through an alkali absorbant in order tb 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 finally pro-
`duce liquified 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 benefit by a process which re-
`duces the energy requirements of producing oxygen
`from air by liqaification.
`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
`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
`
`ing oxygen from gaseous mixtures or water are known.
`Warne et al, U.S. Pat. Nos. 2,217,850, and Folger et al,
`2,450,276, disclose processes of separating oxygen from
`20 other gases using solutions of cobalt compounds. How-
`ever, these techniques would be ineffeotive in a liquid
`system, e.g., seawater, since the compounds are in solu-
`tion and would be washed away if contacted with liq-
`uids rather than the disclosed gases. Miller, U.S. Pat.
`
`25 No. 3,230,045, discloses using oxygen-binding chromo-
`proteins such as hemoglobin and hemocyanin to sepa-
`rate oxygen from other gases. The chromoproteins are
`kept moist or in solution and are immobilized on filter
`paper where they may be bound by a binder such as
`30 fibrin; an electrolyte such as sodium chloride may also
`be present. However, this technique would also be inef-
`fective in a liquid system since the protein is not insolu-
`ble and thus would be washed away if water were al-
`lowed to flow through the system. Moreover, there is
`35 no provision for regeneration of oxidized (inactive)
`oxygen carriers that would be formed in this system.
`Bodetl, U.S. Pat. Nos. 3,333,583, and Robb, 3,369,343,
`disclose apparatus for extracting oxygen from seawater
`using thintubes of silicone rubber or a membrane of
`40 silicone rubber~ respectively. However, neither the cap-
`illary networks nor the permeable membranes working
`alone have been found to be practicable in real-life
`situations, lsomura, U.S. Pat. No. 3,377,777, discloses
`concentrating oxygen from natural waters by equilibra-
`45 tion with exhaled gases, i.e., by utilizing large areas of
`gas-water interface and simple diffusional consider-
`ations 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 solubility of CO2. However,
`55 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 envi-
`ronments comprising a mixture of a metallic superoxide,
`which releases oxygen upon contact with CO2 and
`
`50
`
`60 water vapor, and a material which absorbs CO2. How-
`ever, 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 produc-
`ing oxygen without replenishment, lles et al, U.S. Pat.
`65 No. 4,165,972, discloses separating oxygen from gas
`mixtures using metal chelates as sorbents. However, the
`technique is not extendable to the extraction of oxygen
`from water.
`
`Akermin, Inc.
`Exhibit 1004
`Page 18
`
`

`

`4,602,987
`
`3
`Many compounds in solution have been examined
`with respect to their oxygen absorption properties and
`the mechanistics thereof. The properties of hemoglo-
`bins, hemerythrins and hemocyanins, the naturally oc-
`curring oxygen carriers, have been the subject of nu-
`merous studies, as documented in Bonaventura et al, J.
`Am. Zool., 20, 7 (1980) and 20, I31 (t980). Artificial
`oxygen carriers and their properties in solution are
`described by a number of researchers. Traylor et
`"Solvent Effects on Reversible Formation and Oxida-
`tive Stability of Heine-Oxygen Complexes",
`96, 5597 (1974) discloses the effect of solvent polarity
`on oxygenation of several heine-base complexes pre-
`pared by reduction with sodium dithionite or a mixture
`of Pd black and calcium hydride. Crumbliss et al, *’Mo-
`nomeric Cobalt-Oxygen Complexes", Science, 6, June
`1969, Volume 164, pp. 1168-1170, discloses Schiff base
`complexes of Co(II) which form stable cobalt-oxygen
`species in solution instead of cobalt-oxygen-cobalt
`bridged complexes, Crumbless et al, "Monomeric Oxy-
`gen Adducts of N,N’-Ethylenebis
`(acetylacetoniminato) ligand-cobalt(III): Preparation
`and Properties", J.A.C.S. 92, 55 (!970), discloses a se-
`ries of monomeric molecular oxygen carriers based on
`cobalt ligand complexes. Dufour et al, "Reaction of
`Indoles with Molecular Oxygen Catalyzed by Metallo-
`porphyrius", Journal of Molecular Catalysis, t, 277
`(1980), discloses the catalysis of the oxygenation of
`simple, alkyl-substituted indoles by Co(II), Co(III), and
`Mn(III) meso-tetraphenyl-porphines wherein a ternary
`complex O2-CoTPP-indole is formed initially. Brault et
`al, "Ferrous Porphyrins in Organic Solvents: L Prepa-
`ration and Coordinating Properties", Biochemistry~ 13,
`4591 (1974), discloses the preparation and properties of
`ferrous deutereporphyrin dimethyl ester and ferrous
`mesotetraphenylporphine in various organic solvents.
`Chang et al, "Kinetics of Reversible Oxygenation of
`Pyrloheme-N-[3-( 1-imidazolyl)propyl]amide", dis-
`closes studies on the oxygenation of pyrroheme-N-[3-
`- (l-imidazolyl)propyl]amide, i.e., a synthesized section
`-of the myoglobin active site. Castro, "Hexa and Pen-
`tacoordinate Iron Poryhyrins", Bioinorganic Chemis-
`try, 4, 45-65 (1974), discloses the direct synthesis of
`hexa and pentacoordinate iron porphyrins, i.e., the pros-
`thetic groups for the active sites of certain cytochrome
`and globin heme proteins. Chang et al, "Solution Be-
`havior of a Synthetic Myoglobin Active Site", J.A.C.S.,
`95, 5810 (1973), discloses studies on a synthesized sec-
`tion of the myoglobin active site and indicates that the
`oxygen binding reaction does not require the protein.
`Naturally occurring oxygen carriers have been chemi-
`cally cross-linked and their properties described.
`Bonsen et al, U.S. Pat No. 4,053,590, discloses a poly-
`merized, cross-linked, stromal-free, hemoglobin pro-
`posed to be useful as a blood substitute. Morris et al,
`U.S. Pat No. 4,061,736, discloses intramolecularly
`cross-linked, stromal-free hemoglobin. Wong, U.S. Pat.
`No. 4,064,118, discloses a blood substitute or extender
`prepared by coupling hemoglobin with a polysaccha-
`ride material. Mazur, U.S. Pat. No. 3,925,344, disc!oses
`a plasma protein substitute, i.e., an intramolecular,
`cross-linked hemoglobin composition.
`Numerous papers have been published on immobili-
`zation of hemoglobin and its functional consequences,
`but not in connection with processes for efficient oxy-
`gen extraction from fluids. Vejux et al, "Photoacoustic
`Spectrometry of Macroporous Hemoglobin Particles",
`J. Opt. Soc. Am., 70, 560-562 (1980), discloses glutarat-
`
`4
`dehyde cross-linked hemoglobin and its functional
`properties. The preparation is described as being made
`up of macroporous particles. Hallaway et al, "Changes
`in Conformation and Function of Hemoglobin and
`5 Myoglobin Induced by Adsorption to Silica", BBRC,
`86, 689-696 (1979), discloses that hemoglobin adsorbed
`on silica is somewhat different from hemoglobin in
`solution. The adsorbed form is not suitable for O2 ex-
`traction from liquids. Antonini et al, "’Immobilized
`10 moproteins", Methods of Enzymology, 44, 538-546
`(1976), discloses standard immobilization techniques as
`appIied to hemoglobin and their functional conse-
`quences. Mention is made of hemoproteius bound to
`cross-linked insoluble polysacoharides such as Sepha-
`15 dex or Sepharose, using a pre-activation of the resin
`with CNBr. Rossi-Fanelli et al, "Properties of Human
`Hemoglobin Immobilized on Sepharose 4B", Eur. J.
`Biochemistry, 92, 253-259 (1978), discloses that the
`ability of the hemoglobin to be bound to Sepharose 4B
`20 is dependent upon the eonformational state of the pro-
`tein. Colosimo et at, "The Ethylisocyanate (EIC) Equi-
`librium of Matrix-Bound Hemoglobin", BBA, 328,
`74-80 (1973), discloses Sephadex G-100, Sephadex
`DEAE-AS0 and Sephadex CM-C50 as supports for
`25 human hemoglobin insolubilization. The paper shows
`that the affinity of the insolubilized protein for EIC is
`increased relative to that in solution. Lampe et al, °’Die
`Bindung yon Sauerstoff an tragerfixiertes Hamo-
`gIobin", Aeta Biol. Meal. Germ., 33, K49-K54 (1974),
`30 discloses studies on CM-Sephadex insolubilized hemo-
`globins. Lampe et al, "Der EinfluB der Immobilisierung
`yon Hamoglobin auf dessen Sauerstoffindung", Aeta
`Biol. Meal. Germ., 34, 359-363 (1975), discloses studies
`on CM-Sephadex insolubilized hemoglobins. Pommer-
`35 ening et al, "Studies on the Characterization of Matrix-
`Bound Solubilized Human Hemoglobin", Internao
`tionales Symposium uber Struktur und Funktion der
`Erythrezyten (Rapoport and Jung, ed.), Berlin Akade-
`mie-Verlag Press, 179-186 (1975), discloses Sepharose-
`40 Sephadex types of insolubilization. Brunori et al, "Prop-
`erties of Trout Hemoglobin Covalently Bound to
`Solid Matrix", BBA, 494(2), 426-432, discloses
`pharose 4B or Sephadex G-200, activated by CNBr, to
`immobilize the hemoglobin. Some changes in the rune-
`45 tionaI properties of the hemoglobin were found.
`Various techniques for the insotubihzation (or immo-
`bilization) of biological materials have been developed,
`though not described in conjunction with iusolubitiza-
`tion and utilization of oxygen carriers. Stanley, U.S.
`50 Pat. No. 3,672,955, discloses a technique for the prepa-
`ration of an insoluble, active enzyme, a biological cata-
`lyst, wherein an aqueous dispersion of the enzyme is
`emulsified with a organic polyisocyanate, mixed with a
`solid carrier and the volatile components are then evap-
`55 orated from the mixture. Wood et al, U.So Pat. No.
`3,928,138, discloses a method of preparing a bound
`enzyme wherein, prior to foaming, an isocyanate-
`capped polyurethane is contacted with an aqueous dis-
`person of enzyme under foam-forming conditions,
`60 whereby polyurethane foams containing integrally
`bound enzyme are obtained. Unsworth et al, LI.S. Pat.
`No. 3,928,230, discloses the encapsulation of fluids and
`solids by dissolving a water-insoluble polymerizable
`epoxy monomer in a solvent having high affinity for
`65 water; dispersing the monomer solution in water; dis-
`persing in the so-formed aqueous dispersion the sub-
`stance to be encapsulated; adding a polymerizing agent
`in a solvent having a higher affinity for water than for
`
`Akermin, Inc.
`Exhibit 1004
`Page 19
`
`

`

`4,602,987
`
`6
`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 first electrode compartment of an electro-
`5 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 aft~mity for oxygen, thereby releasing
`free oxygen into said carrier and producing a nonbind-
`10 ing-state oxygen carrier, (5) removing oxygen from said
`carrier fluid to give an oxygen-depleted carrier fluid, (6)
`transporting said oxygen-depleted carrier fluid contain-
`ing said nonbinding-state oxygen carrier to a second
`electrode compartment of an electrochemical cell
`15 which forms a third portion of said closed container,
`and (7) eleetroebemicalty modifying said nonbinding-
`state oxygen carrier to said binding-state oxygen car-
`tier. The invention may also be practiced more broadly
`without carrying out the oxidation and reduction steps
`20 by replacing steps (3)-(7) With the following steps: (3)
`transporting said carder fluid containing said bound
`oxygen complex to a second portion of said closed
`container, (4) removing oxygen from said carrier fluid
`to give an oxygen-depleted carder fluid, and (5) trans-
`25 porting said oxygendepleted carrier fluid into contact
`with said second surface of said membrane. The present
`invention also comprises an apparatus by whioh this
`method can be carried out, which briefly comprises a
`container having a gas permeable membrane which at
`30 least in part defines an inner space of said eon.tainer, a
`carrier fluid as described above in contact with the
`inner surface of the membrane and means for removing
`oxygen from the carrier fluid so that the oxygen can be
`utilized for its desired purpose.
`
`the polymerizing agent; and polymetizing 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 al, 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 prepotymer 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 al, U.S. Pat. No. 3;871,964, discloses
`proteins insotubilized using polymers containing anhy-
`dride, di-methaerylate and a hydrophitie monomer.
`Many of the prior art problems were overcome by
`the invention disclosed in U.S. Pat. Nos. 4,427,4t6 and
`4,343,715, which disclose oxygen eartiers 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 fluid 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 fluids.
`
`SUMMARY OF THE INVENTION
`
`Accordingly, one object of the invention is to pro-
`vide an apparatus capable of extracting oxygen from a
`fluid 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 cyctic 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 fluid
`environment, which comprises the steps of (1) contact-
`ing a first fluid environment containing oxygen with a
`first surface of an oxygen permeable membrane having
`a first and a second surface, wherein said membrane
`separates said env.ironment from an interior space of a
`closed container, (2) contacting a carrier fluid with said
`second surface of said membrane, wherein said carrier
`fluid is confined in said closed container and said carrier
`fluid contains a binding-state oxygen carrier, whereby
`
`35
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`45
`
`A more complete appreciation of the invention and
`many of the attendant advantages thereof will be
`readily obtained as the same becomes better understood
`40 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-
`tess 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
`50 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.
`55 FIG. $ 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
`60 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 countereurrent flow of water and a gas
`65 stream containing carbon dioxide.
`FIG. 8 is a schematic diagram of a device for remov-
`ing carbon dioxide from a gas stream based on a hollow
`fiber cartridge.
`
`Akermin, Inc.
`Exhibit 1004
`Page 20
`
`

`

`7
`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 specific 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. 1~1 shows in graphical form spectra of the oxi-
`dized and reduced forms of an oxygen carrier of the
`invention.
`
`DETAILED DESCRIPTION OF THE
`PREFERRED EMBODIMENTS
`
`The present invention provides a combination of a
`closed membrane system with a reversible oxygen bind-
`ing compound (oxygen carder) on the side of the mem-
`brane isolated from the environment to provide an effi-
`cient system of extracting oxygen. The oxyger, binding
`compound is cycled loading and unloading stations that
`oxygen is loaded onto and unloaded from the oxygen
`carrier at the proper times. Other differences and ad-
`vantages of the present invention are discussed later in
`this specification.
`One key aspect of the present invention is the oxygen
`carder itself. Many oxygen carriers, such as hemoglobin
`and the artificial oxygen carriers described in the prior
`art section of this disclosure, are already known and can
`be used in the practice of the present invention° The
`basic characteristic of an oxygen carrier that can be
`used in the practice of the present inven