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US20110281959A1 - Extraction of Carbon Dioxide and Hydrogen From Seawater and Hydrocarbon Production Therefrom - Google Patents

Extraction of Carbon Dioxide and Hydrogen From Seawater and Hydrocarbon Production Therefrom Download PDF

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US20110281959A1
US20110281959A1 US12/958,963 US95896310A US2011281959A1 US 20110281959 A1 US20110281959 A1 US 20110281959A1 US 95896310 A US95896310 A US 95896310A US 2011281959 A1 US2011281959 A1 US 2011281959A1
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Prior art keywords
seawater
ion exchange
cathode
anode
compartment
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US12/958,963
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Inventor
Feice DiMascio
Dennis R. Hardy
Heather D. Willauer
M. Kathleen Lewis
Frederick Williams
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US Department of Navy
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US Department of Navy
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Priority to US12/958,963 priority Critical patent/US20110281959A1/en
Assigned to U.S.A. AS REPRESENTED BY THE SECRETARY OF THE NAVY, THE reassignment U.S.A. AS REPRESENTED BY THE SECRETARY OF THE NAVY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEWIS, M. KATHLEEN, HARDY, DENNIS R., WILLIAMS, FREDERICK, WILLAUER, HEATHER D., DIMASCIO, FELICE
Priority to PCT/US2011/023708 priority patent/WO2011142854A1/fr
Priority to EP11780946.7A priority patent/EP2569270B1/fr
Publication of US20110281959A1 publication Critical patent/US20110281959A1/en
Priority to US13/838,074 priority patent/US9303323B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/42—Hydrogen of special source or of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to methods and apparatus for extracting carbon dioxide and hydrogen from seawater and to processes for hydrocarbon production including the carbon dioxide extraction method.
  • the hydrogen could be produced through commercial off the shelf conventional electrolysis equipment, and the electrical energy for this process would be derived through nuclear power or Ocean Thermal Energy Conversion (OTEC).
  • OTEC Ocean Thermal Energy Conversion
  • Mohanasundaram S. Renewable Power Generation-Utilising Thermal Energy From Oceans. Enviro. Sci . & Eng. 2007, 4, 35. Avery, W. H.; Wu, C. Renewable Energy From The Ocean ; Oxford University Press: New York, 1994.
  • This synthetic fuel production process could provide an alternative energy source to fossil fuels.
  • the hydration equilibrium constant is 1.70 ⁇ 10 ⁇ 3 . This indicates that H 2 CO 3 is not stable and gaseous CO 2 readily dissociates at pH of 4.5, allowing CO 2 to be easily removed by degassing once the seawater has been acidified to ensure that the unstable H 2 CO 3 is the predominant carbonate species, as discussed above.
  • a detailed composition of seawater shows a carbon concentration of 28 ppm ( ⁇ 100 mg/L as CO 2 ). Assuming that the carbon exists as HCO 3 ⁇ , the HCO 3 ⁇ concentration in seawater will be approximately 142 ppm (0.0023 M), therefore approximately 23 mL of 0.100 M hydrochloric acid is required per liter of seawater:
  • CO 2 exists only in the dissolved gas form when the pH of seawater is decreased to 6 or less Johnson, K. M., King, A. E., Sieburth, J. Coulometric TCO 2 Analyses for Marine Studies: An Introduction. Marine Chem. 1985, 16, 61.
  • a strong cation exchange resin material can be used to acidify the seawater to below pH 6. Hardy, D. H. Zagrobelny, M.; Willauer, H. D.; Williams, F. W. Extraction of Carbon Dioxide From Seawater by Ion Exchange Resin Part I: Using a Strong Acid Cation Exchange Resin ; NRL Memorandum Report 6180-07-9044; Naval Research Laboratory Washington D.C., Apr. 20, 2007.
  • the volume of water per unit weight of resin required to regenerate the resin was much larger than the volume of CO 2 recovered, and potentially larger than the volume of fuel produced from the CO 2 . As a result the approach was deemed impractical for a sea-based application.
  • the present invention relates to an apparatus for seawater acidification.
  • the seawater acidification apparatus includes an ion exchange (IX) compartment, a cathode electrode compartment, an anode electrode compartment and cation-permeable membranes, which separate the cathode and anode electrode compartments from the ion exchange compartment.
  • the apparatus includes a means for feeding seawater through the ion exchange compartment and means for feeding a liquid media capable of dissociating to provide acidic ions through the anode and cathode electrode compartments.
  • the device also includes a cathode located in the cathode electrode compartment, an anode located in the anode electrode compartment and a means for application of current to each of the cathode and anode to create the driving force for the ion exchange process.
  • the present invention relates to a method for the acidification of seawater.
  • seawater is subjected to an ion exchange reaction to exchange H + ions for Na + ions to thereby acidify the seawater.
  • the present invention relates to a method for extracting carbon dioxide from seawater.
  • seawater is subjected to an ion exchange reaction to acidify the seawater to a pH of 6.5 or below by exchange of H + ions for Na + ions in the seawater.
  • carbon dioxide is extracted as bound carbon dioxide in the form of bicarbonate, or the acidified seawater is degassed to obtain gaseous carbon dioxide.
  • the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide.
  • the present invention relates to a method for the production of hydrocarbons from seawater.
  • seawater is subjected to an ion exchange reaction to acidify the seawater to a pH of 6.5 or below by exchange of H + ions for Na + ions in the seawater.
  • the acidified seawater is degassed to obtain gaseous carbon dioxide.
  • the carbon dioxide obtained by degassing is fed to a reactor with hydrogen to produce hydrocarbons.
  • the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide and the hydrogen produced by the ion exchange reaction can be used as a feed stream to the hydrocarbon production step.
  • FIG. 1 is a graph of the total carbonate in seawater as expressed as a function of pH
  • FIG. 2 shows an electrical chemical cell that lowers seawater pH by decomposing water into H + and OH ⁇ , hydrogen gas (H 2 ), and oxygen gas (O 2 ) by means of electrical energy.
  • FIG. 3 is a schematic representation showing the acidification apparatus employed in Example 1 for the process of acidifying seawater.
  • FIG. 4 shows carbon dioxide removal as a function of seawater pH for the CO 2 Degassed Samples of Example 7 ( ⁇ ) and Example 8 ( ⁇ ).
  • FIG. 5 is a graph of the effluent seawater pH as a function of applied current for treatment of Key West Seawater in Example 5 (May 22, 2009) and Example 10 (Nov. 12, 2009).
  • FIG. 6 is a graph of electrical resistance as a function of time showing the effect of scaling in the cathode compartment.
  • FIG. 7 is a schematic diagram of an apparatus for seawater acidification and recovery of carbon dioxide and hydrogen in accordance with the present invention.
  • FIG. 8 is a schematic flow diagram of a carbon dioxide production process in accordance with the present invention.
  • the present invention relates to an apparatus for seawater acidification.
  • the major components of the seawater acidification apparatus 10 shown in FIG. 2 include a central ion exchange (IX) compartment 12 , a cathode electrode compartment 14 , an anode electrode compartment 16 and cation-permeable membranes 18 , 19 which separate the three compartments 12 , 14 , 16 .
  • Seawater is fed to ion exchange compartment 12 via a seawater inlet 20 and removed from ion exchange compartment 12 via a seawater outlet 22 .
  • a fluid capable of dissociating to provide acidic ions, such as water, is fed to each of the cathode and anode electrode compartments 14 , 16 via cathode fluid inlet 24 and anode fluid inlet 26 .
  • the fluid is removed from each of the cathode and anode electrode compartments 14 , 16 via cathode fluid outlet 28 and anode fluid outlet 30 .
  • the apparatus 10 also includes a cathode 32 and an anode 34 . Current is applied to each of the cathode 32 and anode 34 using any conventional electrode apparatus to create the driving force for the ion exchange process.
  • the acidification apparatus 10 in FIG. 2 uses small quantities of electricity to exchange sodium ions for hydrogen ions in a central seawater stream that is flowing adjacent to two cation exchange membranes 18 , 19 .
  • Seawater is passed through the central ion exchange compartment 12 of the apparatus 10 .
  • Sodium ions are transferred through the membrane 18 closest to the cathode 32 and removed from the seawater by means of direct current (DC) voltage.
  • DC direct current
  • These sodium ions are replaced by hydrogen ions as the current drives the ions through the membrane 19 closest to the anode 34 .
  • the hydrogen ions entering compartment 12 cause acidification of the seawater.
  • the anolyte is the water fed to the anode compartment 16 .
  • H + is generated and it must migrate from the surface of the anode 34 , through the cation-permeable membrane 19 , and into the IX compartment 12 where it can replace Na + . Therefore the anolyte must be as dilute as possible such that the H + are in excess and do not compete with any other cations in the anolyte.
  • RO reverse osmosis
  • the anode and cathode may be made of any suitable material, based on cost, chemical stability, electrochemical performance characteristics, and the nature of the process involved.
  • the anode may be made of a conventional material, such as ruthenium and/or iridium oxide on titanium metal, titanium oxide ceramic, and platinum plated titanium.
  • Commercially available anodes of this type include those manufactured by Englehard, Water Star (Newbury, Ohio), Eltech (Chardon, Ohio), and Electrode Products (Union, N.J.).
  • the cathode may be stainless steel or steel. Suitable materials are known to those skilled in the art and selection of a particular anode and cathode material is considered within the skill of those knowledgeable in this field.
  • the cation membrane must selectively pass cations in preference to anions and may be manufactured of any suitable material, based on cost, chemical stability, electrochemical performance characteristics, and the nature of the process involved. Suitable materials are known to those skilled in the art and selection of a particular membrane material is considered within the skill of those knowledgeable in this field.
  • heterogeneous and homogeneous cation membranes that are useful in the present invention include, but are not limited to, cation membranes manufactured or sold by Asahi Chemical, Dupont de Nemours, Membrane International Inc., Sybron/Ionics, Resintech, Ionpure, Hydro Components, Inc., Tulsion, Tokuyama Soda, MEGA as, and PCA-Polymerchemie Altmeier GmbH.
  • membranes formed of perfluorocarbon polymers having cation exchange functional groups that are resistance to oxidation and temperatures. The conditioning and activation can be carried out according to the manufacturer's recommendations.
  • cation exchange resins in the acidification module compartments can serve as an electro-active media that can exchange or absorb sodium ions and release hydrogen ions.
  • the hydrogen ions generated at the anode thus regenerate the resin to the hydrogen form, releasing sodium ions to pass into the adjacent compartment.
  • Their employment is particularly beneficial when feeding dilute solutions in the electrode compartments as they help to lower the module's electrical resistance and increase efficiency.
  • cation exchange resins that are useful in the present invention include, but are not limited to, cation resins manufactured or sold by Mitsubishi Chemical, Dow Chemical, Rohm and Haas Company, Sybron Chemical Inc., Purolite, and Resin Tech Inc.
  • Preferred cation exchange resins are synthetic organic strong acid cation exchange resins that have sulfonated exchange sites as exemplified by standard cross-linked resins, such as IR-120 (Rohm and Haas), as well as high cross-linked resins, such as SK116 (Mitsubishi Chemical).
  • High surface area macro-reticular or micro-porous type ion exchange resins having sufficient ionic conductivity in the catalyst compartment are also suitable.
  • the catholyte is the water fed to the cathode compartment 14 .
  • the catholyte must be free of, or at least substantially free of hardness ions, such as calcium (Ca +2 ), ferrous (Fe +2 ) and magnesium (Mg +2 ).
  • the pH in the cathode compartment 14 is high enough to precipitate these hardness ions. Therefore, a catholyte having a total concentration of hardness ions less than 50 ppm, such as RO permeate or deionized water should be employed.
  • Any suitable means may be employed to feed seawater to the ion exchange compartment 12 and to feed liquid media to the cathode and anode compartments 14 , 16 .
  • Suitable means include pumps and pipes employing gravity feed.
  • Any suitable means may be employed for applying current to cathode and anode 32 , 34 .
  • Suitable means include a power supply or other current generating apparatus.
  • the means for applying charge to the cathode and anode 32 , 34 is capable of reversing the polarity of the cathode and anode 32 , 34 in order to regenerate the acidification apparatus 10 .
  • the maximum acceptable pressure drop limits the minimum size of the particle, which may vary depending on the acidification module design.
  • the pressure drop through any of the compartments in the acidification module is in the range of 0.1 to 100 psi, and is typically between 1 to 10 psi.
  • the size of the particle must be in the mesh size range of ⁇ 1 inch to +60; even more preferably from about ⁇ 1 ⁇ 4 inch to +14; and most preferably from about ⁇ 5 to +7.
  • the flow rate of solution through the ion exchange compartment is not critical and can be selected from a broad range. However, the flow rate can be controlled to produce a controlled seawater pH.
  • the velocity of the solution through the ion exchange compartment should be at a level where adequate agitation or stirring of seawater through the compartment is achieved. A velocity between 10 to 500 cm/min; more preferably from 30 to 210 cm/min; most preferably from 60 to 90 cm/min may be employed.
  • the process in accordance with this invention is operated at a current density in the range of 5 to 200 mA/cm 2 ; more preferably from about 20 to 100 mA/cm 2 ; and most preferably from about 50 to 70 mA/cm 2 .
  • FIG. 3 shows an alternative apparatus 50 for the acidification of seawater including a pump 202 for feeding seawater from a tank 201 to the ion exchange compartment 12 of ion exchanger 208 .
  • Softened or deionized water is fed from a tank 203 using a pump 205 to the cathode and anode compartments 14 , 16 .
  • a power supply 209 is provided to apply a current to the cathode and anode 32 , 34 of ion exchange apparatus 208 .
  • Acidified sweater is obtained from the ion exchange compartment 12 and a mixture of sodium hydroxide, oxygen and hydrogen is obtained from the cathode and anode compartments 14 , 16 .
  • FIG. 2 shows an acidification apparatus 10 which can be employed to exchange Na + for H + in a stream that is flowing adjacent to two cation-permeable membranes 18 , 19 .
  • a small amount of electricity facilitates this exchange.
  • the amount of H + generated is proportional to the applied electrical current, which follows Faraday's constant.
  • Faraday's constant is defined as the amount of electricity associated with one mole of unit charge or electron, having the value 96,487 ampere-second/equivalent.
  • Current efficiency can be defined as the ratio of the theoretical minimum current predicted by Faraday's law to the actual current applied to the electrodes of the acidification apparatus 10 . In actuality, current efficiencies are never 100% and can range from 30 to 95% based on the conductivity of the liquid being treated; the higher the conductivity, the greater the current efficiency. It is estimated that current efficiency for seawater is on the order of 70-90%. Therefore,
  • the theoretical amount of CO 2 that can be removed from the acidified seawater is 0.0023 moles per liter. Removal efficiency can be defined as the ratio of the theoretical amount of CO 2 removed to the actual amount of CO 2 removed in the acidified seawater. Removal efficiencies are never 100% and can range from 50-95% based on various unit operating requirements. The overall removal of CO 2 is conservatively estimated to be approximately 50%.
  • the molar ratio of H 2 and CO 2 is 0.32. Increasing the current increases the molar ratio of hydrogen to carbon dioxide with no effect on the operation of the acidification apparatus 10 .
  • H + generated will either exchange with Na + in the seawater to further lower its pH or migrate through the IX compartment 12 and into the cathode compartment 14 where it will combine with OH ⁇ to form water.
  • Bound CO 2 can be captured from seawater in the form of bicarbonate.
  • CO 2 in seawater of pH of less than 4.5 can be naturally and completely degassed upon exiting the acidification cell by exposure to the atmosphere.
  • CO 2 in seawater having a pH greater than 4.5 may require assistance to degas, by, for example, vacuum degassing for complete CO 2 removal.
  • the degree of vacuum degassing required to completely remove CO 2 increased as the seawater pH increased.
  • the cation exchange resin can be electrolytically regenerated, allowing simultaneous and continuous ion exchange and regeneration to occur within the apparatus. This eliminates the need for regeneration by caustic chemicals that are not ideal for a sea-based application.
  • the degree of ion exchange and regeneration within the cell is a function of the current applied. Lowering the pH of seawater is an electrically driven membrane process, where seawater pH is proportional to applied current and independent of the media contained within the IX compartment.
  • the examples below show that carbon dioxide was readily removed from seawater at pHs of less than 6.0. Unassisted and near complete degassing was observed in seawater samples of pH of 5.0 and less. Assisted degassing by vacuum was required in seawater samples at pHs of greater than 5.0.
  • the apparatus produced a portion of the hydrogen needed for a hydrocarbon synthesis process with no additional energy penalty.
  • the production of hydrogen gas at the cathode as a byproduct occurred at a rate that correlated with the applied current.
  • the applied current to the apparatus can be increased to generate more hydrogen gas with no negative performance or operational effects on the acidification process.
  • the acidification apparatus' ability to produce a portion of the hydrogen needed for the downstream synthesis of hydrocarbons from the recovered carbon dioxide reduces the operational footprint of the process, thus making the technology more feasible for a sea-based application.
  • the present invention relates to a method for the acidification of seawater.
  • seawater is subjected to an ion exchange reaction to exchange H + ions with Na + ions in the seawater to thereby acidify the seawater.
  • the seawater is acidified to a pH of less than about 6.5, more preferably, to a pH of less than about 6.0, even more preferably to a pH of less than about 5.0 and, most preferably, to a pH of less than about 4.5.
  • Acidification of the seawater causes carbonic acid formation in the seawater, which allows for recovery of carbon dioxide from the acidified seawater.
  • Bound carbon dioxide can be removed from the acidified seawater in the form of bicarbonate.
  • the acidified seawater can be degassed to obtain carbon dioxide.
  • Acidified seawater can be directly degassed by exposure to atmosphere if the pH of the acidified seawater is less than about 5.0 and, greater recoveries of carbon dioxide can be obtained if the pH of the acidified seawater is less than about 4.5.
  • degassing may be assisted by, for example, application of a vacuum.
  • a suitable apparatus for degassing acidified seawater is a vacuum stripper. Any other device that is capable of creating a vacuum such that the gas pressure is substantially less than atmospheric pressure may be employed.
  • the apparatus 200 includes a pump 202 which pumps raw seawater through a filter 204 , preferably having pores of about 5 microns to filter particulate matter from the seawater.
  • the filter 204 is optional, though preferred to reduce the potential for fouling, especially in embodiments employing seawater reverse osmosis device 206 .
  • the filtered seawater may then be fed to the ion exchanger 208 , as shown.
  • a portion of the filtered seawater may be fed to the seawater reverse osmosis device 206 and a portion of the filtered seawater may be fed to the ion exchanger 208 .
  • Ion exchanger 208 is provided with a power supply 209 with the capability of reversing the polarity of electrodes 32 , 34 for regeneration of ion exchanger 208 .
  • Ion exchanger 208 functions as an acidification cell for acidification of the seawater fed to ion exchange compartment 12 via seawater inlet 20 as described above in relation to FIG. 2 .
  • the process may provide both carbon dioxide and hydrogen gas, depending upon the specific conditions employed in ion exchanger 208 .
  • any module configuration can be used in accordance with this invention.
  • Such configurations include, but are not limited to, spiral and cylindrical tube designs.
  • Module orientation, or positioning of the electrodes, may be horizontal or vertical.
  • the thickness of the ion exchange compartment 12 can be varied depending on the desired module performance.
  • the ion exchange compartment 12 thickness may be adjusted depending on operating parameters, such as flow rate, temperature, etc., and/or desired reactor performance, such as product pH, electrical resistance, etc., and is typically between 0.3 to 10.0 cm.
  • the width of the chamber defining the ion exchange compartment may be adjusted depending on operating parameters and desired module performance, and the width to thickness ratio is typically between 5 and 20. There is no limit on the length of the chamber other than as dictated by practical construction and fluid pressure loss considerations.
  • Solution can be passed through any of the compartments in the electrolytic reactor from bottom to top or from top to bottom.
  • the flow direction in two adjacent compartments can be co-current or counter-current.
  • Solution can be passed in parallel through each compartment, or a least one stream may flow in series through at least two compartments.
  • the components of the acidification module 200 may be made from a polymeric (plastic) material that is chemically resistant and non-conductive.
  • a polymeric (plastic) material that is chemically resistant and non-conductive.
  • Such materials include, but not limited to, PVC, chlorinated PVC, ABS, KynarTM, TeflonTM, and other fluoropolymers.
  • the closing or sealing of the acidification module 200 can be achieved using tie-bars, hydraulic or pneumatic type presses, or by solvent or adhesive bonding.
  • the method 300 involves the steps of providing seawater 302 and filtering seawater 304 .
  • Filtered seawater is fed to ion exchange compartment 12 of ion exchanger 208 and subjected to an ion exchange step 306 to acidify the seawater.
  • a portion of the filtered seawater may be subjected to a seawater reverse osmosis step 308 and the permeate of this step may be fed to the cathode and anode compartments 14 , 16 of ion exchanger 208 for use as the ion exchange fluid in ion exchange step 306 .
  • Acidified seawater produced in ion exchange step 306 may then be fed to degassing step 310 to separate carbon dioxide from the acidified seawater.
  • the ion exchange fluids from cathode and anode compartments 14 , 16 may be fed to stripping step 312 to separate hydrogen from the ion exchange fluids.
  • Carbon dioxide produced by the process of the present invention may be fed to a reactor for the production of hydrocarbons such as jet fuels.
  • the carbon dioxide may be used in industrial and marine fire extinguishing systems.
  • Hydrogen produced by the process of the present invention may also be fed to the same hydrocarbon production reactor or alternatively, may be used for other purposes, such as fuel.
  • the polarity of the electrodes 32 , 34 of the ion exchanger 208 may be reversed from time to time in ion exchange step 306 to regenerate ion exchanger 208 .
  • an electrochemical acidification cell has been developed, tested, and found to be practical for recovering large amounts of CO 2 from seawater for use as a carbon feedstock in a sea-based fuel production process.
  • the anode used in the NalcoTM cell is a dimensionally stable anode (DSA) composed of a mixed precious metal oxide coating on titanium.
  • the IonpureTM cell uses a platinum plated titanium anode.
  • each cell contains a different type of cation-permeable membrane.
  • the NalcoTM cell contains Sybron's MC3470TM reinforced/casted cation permeable membrane, while the IonpureTM cell contains a polyethylene extruded cation permeable membrane.
  • Ionpure TM Cell Configured as an Electrochemical Acidification Cell Dimensions Approximate Overall Cell 33 cm ⁇ 61 cm ⁇ 8 cm Dimension IX Compartment Width 14 cm IX Compartment Height 35.5 cm IX Compartment Thickness 0.9 cm IX Compartment Volume 429 cm 3 Membranes Active Area 497 cm 2 Electrode Compartment Volume 214 cm 3 Electrical Specifications Electrode Active Area 497 cm 2 Max. Current Density 400 A m ⁇ 2 Flow Specifications Max. Flow Rate 35 cm 3 s ⁇ 1 Max. Electrolyte Flow Rate 35 cm 3 s ⁇ 1 Max. Operating Temperature 60° C. Max. Operating Pressure 350 kPa Materials Anode (Platonized Titanium) Cathode 316L Stainless Steel Membrane Ionpure Cation-Permeable Membrane Molded Frame and End Block Polyethylene (PE)
  • PE End Block Polyethylene
  • FIG. 3 is a schematic representation of the acidification experimental set-up.
  • Seawater was passed upwardly through the ion exchange (IX) compartment.
  • Deionized water at a pH of approximately 6.7 was passed, in series, upwardly through the anode compartment and then upwardly through the cathode compartment.
  • a controlled current was applied to the anode and cathode in order to lower the pH of the seawater to the target level. Only a single pass of seawater and deionized water through the cell was employed.
  • IO-1 Synthetic seawater was prepared by dissolving 41.1 gL ⁇ 1 of Instant Ocean Sea Salt in deionized water at a total volume of 100 liters.
  • the pH of the synthetic seawater was 9.1 ⁇ 0.5.
  • the CO 2 content was not measured.
  • IO-2 Synthetic seawater was prepared by dissolving 35 gL ⁇ 1 of Instant Ocean Sea Salt in deionized water at a total volume of 140 liters.
  • the pH of the synthetic seawater was 8.4 ⁇ 0.2.
  • the CO 2 content was not measured.
  • IO-3 Synthetic seawater, made using Instant Ocean Sea Salt at 35 gL ⁇ 1 , was supplemented with 90 ppm of sodium bicarbonate and diluted with deionized water to a total volume of 140 liters.
  • the pH of the synthetic seawater was 8.2.
  • the CO 2 content was measured to be approximately 100 ppm.
  • IO-4 Synthetic seawater, made using Instant Ocean Sea Salt at 35 gL ⁇ 1 , was supplemented with 90 ppm of sodium bicarbonate and diluted with deionized water to a total volume of 140 liters.
  • the pH was adjusted to 7.6 using approximately 20 mLs of diluted hydrochloric acid (5 mL of concentrated HCl diluted to 50 mL) added to 100 liters of synthetic seawater.
  • the CO 2 content was measured to be approximately 100 ppm.
  • Degassing measurements were made on selective samples during the course of the experiment. For each measurement carbon dioxide was degassed from solution using a Brinkmann Roto-Evaporator. A 20 mL sample was placed in a 1000 mL round bottomed flask and rotated at an rpm setting of 8 for five minutes. A water aspirator was used to provide a vacuum of approximately 15 mm Hg.
  • the NalcoTM cell (Table 1) was configured such that a strong acid cation exchange resin was used to fill both the ion exchange compartment (IX) and the electrode compartments shown in FIG. 2 .
  • IO-1 seawater was used as the influent, and passed through the IX compartment at 140 ml/min for 165 minutes.
  • the flow rate of the deionized water passing through the electrode compartments was increased to a final flow rate of 140 mL/min.
  • Table 3 show that when 3 amps of current where applied to the cell, the pH of the effluent seawater was lowered to between 2.08 and 2.15. As the current was decreased from 3 to 0.25 amps, the pH of the effluent seawater was increased to 5.88.
  • O-2 was used to determine the effect that flow rate through the IX compartment had on the performance of the NalcoTM cell.
  • IO-2 was pumped at 900 mL/min before a flow of 860 mL/min was established and maintained after 90 minutes.
  • Table 4 establish that at higher flow rates the pH of the effluent seawater can be lowered using the acidification cell. Higher influent seawater flow rates increase the percent recovery from 50% to 86%.
  • the results indicate that the flow rate to current ratio was improved from 560 to 716 (860 mL/min/1.20 amps).
  • the third example examines the effects of replacing the strong cation exchange material in the IX compartment of the cell with inert ceramic particles.
  • the affects of the ceramic media on the ion exchange efficiency of Na + for H + ions in the cell is determined in the results shown in Table 5.
  • the pH of IO-2 is reduced from 8.29 to 6.3 in 150 minutes. Since the pH of the IO-2 water can be lowered with inert media in the IX compartment the process is considered to be an electrically driven membrane process.
  • the progressive decrease in the IO-2 pH indicates that the cation exchange resin in the anode compartment was regenerating. Since the cation exchange resin in the anode compartment was in the sodium form during the start of the experiment and that H + ions from the oxidation of water on the anode exchanged on the resin and released Na + ions. These Na + ions then migrated through the cation exchange membrane and into the IX compartment.
  • Breakthrough of H + ions into the IX compartment began at 60 minutes when the pH of the seawater began to decrease. See FIG. 1 for illustrative details.
  • the high and stable pH of the NaOH is a result of this.
  • the flow rate to current ratio was further improved from 716 to 755 (680 mL/min/0.90 amps) at a recovery of 83% using this process.
  • a new IO formulation (IO-3) was made that had a similar alkalinity concentration as that found in KW seawater. However, the pH was 8.19 compared to the 7.67 measured for the KW seawater. Table 8 shows that the amount of current required to reduce the pH of IO-3 from 8.19 to 6.0 was approximately three times higher than that seen in previous example. The flow rate to current ratio was approximately 111 (140 mL min ⁇ 1 /1.26 amps), which is lower than the theoretical ratio of 267. The recovery was between 88% and 95%. The CO 2 content in IO-3 was found to be adequate so the low ratio may be attributed to the acidification cell not having been operated long enough to reach equilibrium.
  • a new IO formulation for example 7 was made in an effort to create a synthetic system that had a similar pH and alkalinity to KW seawater.
  • IO-4 was used to challenge the acidification cell, the results shown in Table 9 indicate that the amount of current required to reduce the pH to 6.0 was approximately two times higher (0.47 vs 0.89 amps).
  • the flow rate to current ratio was approximately 157 (140 mL/min/0.89 amps), which is lower than the theoretical ratio of 267.
  • the recovery at these flow rates was between 88% and 95%.
  • the CO 2 content in IO-4 was found to be adequate so the low ratio may be attributed to the acidification cell not having been operated long enough to reach equilibrium.
  • Example 8 Demonstrating the feasibility of scaling this process was the objective of Example 8 (Table 10).
  • the larger IonpureTM cell (Table 2) was configured similarly to the NalcoTM cell used in Examples 3-7.
  • IO-4 was used to challenge the cell at a flow rate of 1050 mL/min to the IX compartment. From Table 10 the amount of current required to reduce the pH from 7.6 to 4.5 was approximately 4.87 amps. The flow rate to current ratio was approximately 216 (1050 mL min ⁇ 1 /4.87 amps). This ratio is lower than the theoretical ratio of 267. The recovery was 90%. Since the CO 2 content in IO-4, was similar to that measured in KW seawater, the low ratio may be attributed the acidification cell not having been operated long enough to reach equilibrium.
  • Example 9 The IonpureTM cell was re-configured in Example 9 (Table 11) such that no material was used in IX compartment of the cell. Table 11 shows that the results were consistent with the results of Example 8 (Table 10) during the first 100 minutes of operation which further indicates that this process is an electrically driven membrane process, whereby the media contained in the IX compartment has no effect on the acidification of the seawater.
  • voltage and flow rate irregularities occurred indicating internal disruption due to non-supported membranes.
  • the pH began to increase and the flow rate began to decrease in the IX compartment while the flow rate increased and pH decreased in the electrode compartments, indicating a gross leak between compartments.
  • Example 9 Towards the end of this Example 9 (Table 11), a crude electrode gas (H 2 and O 2 ) capture experiment was performed, but both gases were captured together due to a common electrode compartment inlet and outlet. The combined gas captured was approximately 10 mL/min per amp. This is close to theoretical according to Faraday's law which indicated an expected value of 10.5 ml/min (7.0 mL/min H 2 +3.5 mL/min O 2 ) per amp at the standard conditions of temperature and pressure.
  • the pH of the effluent acidified seawater was measured for each of Examples 1-9.
  • the effluent acidified seawater was collected and 20 mL aliquots were placed in a 1000 mL round bottom flask and degassed using a Brinkmann Roto-Evaporator.
  • a water aspirator provided a vacuum of approximately 15 mm Hg.
  • the carbon dioxide content of each solution was measured by coulometry and plotted as a function of pH, as shown in FIG. 4 .
  • greater than 98% carbon dioxide removal was achieved at pHs lower than 4.5.
  • CO 2 dissolved in water is in equilibrium with H 2 CO 3 .
  • CO 2 in seawater samples of pH of less than 4.5 was naturally and completely degassed upon exiting the acidification cell (exposed to atmosphere during sampling). CO 2 content and pH were measured before and after vacuum degassing and there was no significant difference in these two measurements.
  • CO 2 in seawater samples having a pH greater than 4.5 required assistance by vacuum degassing for complete CO 2 removal.
  • CO 2 content and pH were measured before and after vacuum degassing and there were significant differences in both measurements; CO 2 content decreased and pH increased. Although not quantified, it appeared that the degree of vacuum degassing required to completely remove the CO 2 increased as seawater pH increased.
  • Example 10 was conducted to confirm the results of acidification of KW seawater obtained in Example 5. The process was also scaled up by five times to determine if the process can be linearly scaled up.
  • Example 5 The acidification process of Example 5 was continued and operated for an additional 105 minutes in this Example 10.
  • Example 10 (Nov. 12, 2009) were consistent with the results of Example 5 (May 22, 2009), while keeping all variables and operating conditions identical.
  • Example 5 A theoretical flow rate to current ratio was used to evaluate the experimental results.
  • Example 5 KW seawater had a ratio of 298 with the NalcoTM module (140 mL/min required 0.47 amps to lower the pH to below 6.00). This ratio will be used to determine if the process can be scaled up in a linear fashion.
  • the dimensions of the IX compartment were 0.050 m ⁇ 0.301 m ⁇ 0.120 m, giving an area of 0.015 m 2 and a volume of 0.001 m 3 .
  • the NalcoTM module was operated at 140 mL/min or 0.037 gpm, giving the following two ratios:
  • Example 11 was conducted at a higher flow rate to demonstrate that the scale up is linear.
  • the same NalcoTM module was operated at five times more flow rate (700, mL/min) using KW seawater.
  • the flow rate to current ratio was 298 (700 mL/min required 2.35 amps to lower the pH to 5.34).
  • the two flow rate ratios were:
  • the particle size of the inert media can be increased from, for example, 20 to 40 mesh (0.41 to 0.76 mm) to 7 to 14 mesh (1.52 to 2.79 mm) in order to reduce the pressure drop.
  • Hardness contained in seawater includes calcium (Ca +2 ) and magnesium (Mg +2 ) ions, and their total ion concentration is typically less than 2,000 mgL ⁇ 1 .
  • Hardness ions can migrate from the ion exchange (IX) compartment to the cathode compartment and can be introduced into the cathode compartment by the water feeding the cathode compartment.
  • IX ion exchange
  • deionized water was used as the feed water to the cathode compartment, so the only hardness ions entering the cathode compartment were from the IX compartment. It was initially assumed that the likelihood of hardness ions migrating from the IX compartment to the cathode compartment was negligible for the following three reasons:
  • FIG. 6 is a plot of electrical resistance (voltage divide by amperage) versus time. The signs of scaling are visible as a progressive increase in the electrical resistance over time. There was a 58.5% increase in electrical resistance (from 4.07 to 6.45 Ohms) after 150 minutes of operation. Reversing the polarity of the electrodes every 15 to 20 minutes can reduce fouling. This change in polarity causes scale and organics to disassociate from the electrode surface. The flow will also have to switch during every polarity reversal. This can be accomplished using solenoid valves that are synchronized to the polarity reversal. This is a common feature that is used in the Electrodialysis Reversal (EDR) process to desalinate brackish water.
  • EDR Electrodialysis Reversal

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US20160215403A1 (en) 2016-07-28
US11421331B2 (en) 2022-08-23
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EP2569270B1 (fr) 2019-10-09
WO2011142854A1 (fr) 2011-11-17

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