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WO2002036859A1 - Methodes permettant d'ameliorer la conductivite ionique dans le dioxyde carbone et ses melanges - Google Patents

Methodes permettant d'ameliorer la conductivite ionique dans le dioxyde carbone et ses melanges Download PDF

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Publication number
WO2002036859A1
WO2002036859A1 PCT/US2001/045574 US0145574W WO0236859A1 WO 2002036859 A1 WO2002036859 A1 WO 2002036859A1 US 0145574 W US0145574 W US 0145574W WO 0236859 A1 WO0236859 A1 WO 0236859A1
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Prior art keywords
carbon dioxide
composition
mixtures
matter
group
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PCT/US2001/045574
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English (en)
Inventor
Peter S. Fedkiw
Jin Jun
Joseph M. Desimone
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North Carolina State University
University Of North Carolina At Chapel Hill
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Publication of WO2002036859A1 publication Critical patent/WO2002036859A1/fr

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/11—Electrochemical processes, e.g. electrodialysis
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances

Definitions

  • the invention generally relates to compositions of matter which include carbon dioxide and exhibit increased ionic conductivity, along with methods of increasing the ionic conductivity of such compositions of matter.
  • Electrochemical processes are currently gaining an increased amount of attention due to their ability to be potentially employed in a wide number of applications.
  • electrochemical oxidation in principal is a potentially more environmentally benign route for the destruction of chemical waste in comparison to thermal oxidation or wet-chemistry techniques. Specifically, the generation of noxious off-gases is minimized if not entirely eliminated, and mineral acids and salts are typically created by the electrooxidation of hetero-atom organics.
  • refractory chemicals may be destroyed at relatively mild processing conditions by supplying adequate energy through the cell voltage.
  • electrochemical synthesis is believed to be a viable
  • the electrodes themselves may be capable of functioning as the site for oxidation and reduction. Consequently, spent chemical agents are usually not generated, and accompanying separation processes are typically not necessary.
  • controlling the electrical current may set the rate of reaction, or alternatively, the electrode potential can be controlled to obtain specificity for the desired product(s). See e.g., D. Genders and N. Weinberg (eds.)
  • Electrochemical processes for waste destruction or chemicals manufacture in a supercritical fluid (SCF) presents a potential opportunity to couple and exploit the tunable solvent properties of SCFs with the controllability of electrochemical reactions.
  • SCF media e.g., water, ammonia, acetonitrile, carbon dioxide, and sulfur dioxide.
  • SCF media e.g., water, ammonia, acetonitrile, carbon dioxide, and sulfur dioxide.
  • the invention provides a composition of matter comprising an ionic compound; and a carbon dioxide containing fluid having at least one salt dissolved therein comprising at least one C0 2 -phi!ic segment.
  • the carbon dioxide containing fluid displays a higher ionic conductivity relative to a carbon dioxide containing fluid that does not contain the at least one salt.
  • the invention provides a process which utilizes the composition of matter described herein.
  • the invention provides a method for increasing the ionic conductivity of a carbon dioxide-containing fluid. The method comprises introducing a salt into the carbon dioxide-containing fluid such that the salt dissolves therein to increase the ionic conductivity of the carbon dioxide- containing fluid dissolved therein.
  • the salt comprises at least one CO 2 -philic segment.
  • FIG. 1 A is a schematic diagram illustrating an example of an apparatus
  • FIG. 1B is a schematic diagram illustrating an example of an electrode which may be employed in conjunction with the invention.
  • FIG. 2 is a schematic diagram of a high pressure vessel that can be used in accordance with the invention.
  • FIGS. 3A-3C are graphs illustrating the effects of pressure, temperature, and types of salt on conductivity of mixtures comprising 5 mmol of: (a) LiCF 3 C0 2 (FIG. 3A), (b) NaCF 3 CO 2 (FIG. 3B), and (c) KCF 3 CO 2 (FIG. 3C).
  • FIGS.4A-4C are graphs illustrating the effects of pressure, temperature, and types of salt on conductivity of mixtures comprising 0.5 mmol of: (a) LiCF 3 CO 2 (FIG. 4A), (b) NaCF 3 CO 2 (FIG. 4B), and (c) KCF 3 CO 2 (FIG. 4C).
  • FIGS. 5A-5C are graphs illustrating the effects of pressure, temperature, and types of salt on conductivity of mixtures comprising 0.05 mmol of: (a) LiCF 3 CO 2 (FIG. 5A), (b) NaCF 3 CO 2 (FIG. 5B), and (c) KCF 3 CO 2 (FIG. 5C).
  • FIGS. 6A-6B are graphs illustrating the effects of temperature on the conductivity of mixtures comprising 0.5 mmol of salt.
  • FIG. 6A illustrates the effect of temperature vs. conductivity.
  • FIG. 6B illustrates the effect of temperature vs. pressure.
  • FIGS. 7A-7B are graphs illustrating the effects of temperature on the conductivity of mixtures comprising 0.05 mmol of salt.
  • FIG. 7A illustrates the effect of temperature vs. conductivity.
  • FIG. 7B illustrates the effect of temperature vs. pressure;
  • FIG. 8 is a graph illustrating the temperature dependence of the molar conductivity for mixtures comprising 0.05 mmol and 0.5 mmol of perfluorinated salts.
  • FIG. 9 is a graph illustrating the conductivities of mixtures comprising 5 mmol of lithium trifluoroacetate and lithium acetate at each temperature as a function of C0 2 pressure.
  • FIG. 10 is a graph illustrating the conductivities of mixtures comprising 0.05 mmol of lithium trifluoroacetate and lithium acetate at each temperature as a function of CO 2 pressure.
  • the invention relates to a composition of matter.
  • the composition of matter comprises an ionic compound and a carbon dioxide containing fluid having at least salt dissolved therein.
  • the salt comprises at least one CO 2 -philic segment, and thus is soluble in the carbon dioxide.
  • the carbon dioxide containing fluid displays a higher ionic conductivity relative to a carbon dioxide containing fluid that does not contain the at least one salt.
  • the composition of matter is homogeneous (i.e., single-phase). Any number of ionic compounds may be used for the purposes of the invention.
  • the cations that can be employed are numerous and known to those skilled in the art.
  • Exemplary cations include, without limitation, a metal cation, particularly those which are alkali metals (e.g., sodium, lithium, potassium), alkaline earth metals, transition metals, rare earth metals, and mixtures thereof.
  • Exemplary anions include, without limitation, halogens, hydroxyl, carbonate, phosphate, acetate, trifluoroacetate, and the like.
  • the composition of matter preferably comprises from about 0.1 , 0.5, 1, or 3 to about 6, 8, 9, or 10 percent by weight of the ionic compound.
  • carbon dioxide is employed as a fluid in a liquid or supercritical phase.
  • the temperature employed during the process is preferably below 31 °C.
  • the CO 2 is utilized in a "supercritical" phase.
  • "supercritical" means that a fluid medium is above its critical temperature and pressure, i.e., about 31 °C and about 71 bar for CO 2 .
  • the thermodynamic properties of CO 2 are reported in Hyatt, J. Org. Chem. 49: 5097-5101 (1984); therein, it is stated that the critical temperature of CO 2 is about 31 °C; thus the present invention may be carried out at a temperature above 31 °C.
  • CO 2 -philic segment refers to the segment having an affinity or capable of being solubilized in carbon dioxide.
  • Various CO 2 -philic segments may be employed including fluorinated segments (e.g., fluorinated polyethers, fluoroalkyls, and fluorinated polyacrylates), perfluorinated segments, silicon-containing segments (e.g., siloxanes), and mixtures thereof. Examples include, but are not limited to, those set forth in U.S. Patent Nos. 5,676,705; and 5,683,977 to Jureller et al., the disclosures of which are incorporated herein by reference in their entirety.
  • perfluorinated salts can be used for the purposes of the invention which contain C0 2 -philic segments and which are soluble in the carbon dioxide.
  • perfluorinated salt refers to one which has at least one perfluorinated group.
  • perfluorinated salts include, without limitation, a perfluoro alkyl sulfonate, a perfluoro alkyl carboxylate, a perfluoro sulfonyl imide, a perfluoro methide, and mixtures thereof.
  • Exemplary perfluoro alkyl sulfonates are of the formula:
  • n ranges from 1 to 10 and M is a cation with a +1 charge including, without limitation, those described herein.
  • Exemplary perfluoro alkyl carboxylates are of the formula:
  • n ranges from 1 to 10 and M is a cation with a +1 charge including, without limitation, those described herein.
  • Exemplary perfluoro imides are of the formula:
  • n ranges from 1 to 10 and M is a cation with a +1 charge including, without limitation, those described herein.
  • Exemplary perfluoro methides are of the formula:
  • composition of matter comprises from about 0.1 to about 10 percent by weight of the perfluorinated salt.
  • composition of matter also may optionally comprise at least one co-solvent.
  • co-solvents can be used, and preferably co-solvents which have a dielectric constant greater than supercritical state of carbon dioxide.
  • polar co- solvents are used.
  • co-solvents that could be used include, but are not limited to, alcohols (e.g., methanol, ethanol, and isopropanol); water; nitriles (e.g., acetonitrile); fluorinated and other haiogenated solvents (e.g., chlorotrifluoromethane, trichlorofluoromethane, perfluoropropane, chlorodifluoromethane, and sulfur hexafluoride); amines (e.g., N-methyl pyrrolidone); amides (e.g., dimethyl acetamide); esters (e.g., ethyl acetate, dibasic esters, and lactate esters); ethers (e.g., diethyl ether, tetrahydrofuran, and glycol ethers); ketones (e.g., acetone and methyl ethyl ketone); organosilicones; al
  • composition of matter preferably comprises from about 5 to about 20 percent by weight of co-solvent.
  • composition of matter of the invention may optionally include a surfactant.
  • surfactants that can be used include, without limitation, neutral surfactants, ionic surfactants, as well as surfactants that contain at least one "C ⁇ 2 -philic" segment.
  • Preferred surfactants include those containing at least one fluorinated segment (e.g., fluorinated or perfluorinated surfactants).
  • the surfactants which are employed are known to those skilled in the art. Examples of suitable surfactants are set forth in U.S. Patent Nos.
  • CO 2 -philic segments may include a halogen (e.g., fluoro or chloro)-containing segment, a siloxane-containing segment, a branched polyalkylene oxide segment, or mixtures thereof. Examples of "CO 2 -philic" segments are set forth in U.S. Patent Nos. 5,676,705; and 5,683,977 to Jureller et al.
  • the fluorine-containing segment is typically a "fluoropolymer".
  • a "fl ⁇ oropolymer” has its conventional meaning in the art and should also be understood to include low molecular weight oligomers, i.e., those which have a degree of polymerization greater than or equal to two. See generally Banks et al., Organofluorine Compounds: Principals and Applications (1994); see also Fluorine-Containing Polymers, 7 Encyclopedia of Polymer Science and Engineering 256 (H. Mark et al. Eds. 2d Ed. 1985).
  • fluoropolymers are formed from monomers which may include fluoroacrylate monomers such as 2-(N-ethylperfiuorooctane- sulfonamido) ethyl acrylate (“EtFOSEA”), 2-(N-ethylperfluorooctane- sulfonamido) ethyl methacryiate (“EtFOSEMA”), 2-(N-methylperfluorooctane- sulfonamido) ethyl acrylate (“MeFOSEA”), 2-(N-methylperfluorooctane- sulfonamido) ethyl methacryiate (“MeFOSEMA”), 1,1'-dihydroperfluorooctyl acrylate (“FOA”), 1,1'-dihydroperfluorooctyl methacryiate (“FOMA”), ⁇
  • Copolymers using the above monomers may also be employed.
  • exemplary siloxane- containing segments include alkyl, fluoroalkyl, and chloroalkyl siloxanes. More specifically, dimethyl siloxanes and polydimethylsiloxane materials are useful. Mixtures of any of the above may be used.
  • the "CO 2 -philic" segment may be covalently linked to the "C0 2 -phobic" segment.
  • Surfactants that are suitable for the invention may be in the form of, for example, homo, random, block (e.g., di-block, tri-block, or multi-block), blocky (those from step growth polymerization), and star homopolymers, copolymers, and co-oligomers.
  • Exemplary homopolymers include, but are not limited to, poly(1 ,1'-dihydroperfluorooctyl acrylate) ("PFOA”), poly(1.1'-dihydro- perfluorooctyl methacryiate) (“PFOMA”), poly(2-(N-ethylperfluorooctane- sulfonamido) ethyl methacryiate) (“PEtFOSEMA”), and poly(2-(N- ethylperfiuorooctane sulfonamido) ethyl acrylate) (“PEtFOSEA”).
  • PFOA poly(1 ,1'-dihydroperfluorooctyl acrylate)
  • PFOMA poly(1.1'-dihydro- perfluorooctyl methacryiate)
  • PFOSEMA poly(2-(N-ethylper
  • Exemplary block copolymers include, but are not limited to ' , polystyrene-b-poly(1 ,1- dihydroperfluorooctyl acrylate), polymethyl methacryiate-b-poly(1,1- dihydroperfluorooctyl methacryiate), poly(2-(dimethylamino)ethyl methacrylate)-b-po!y(1,1 -dihydroperfluorooctyl methacryiate), and a diblock copolymer of poly(2-hydroxyethyl methacryiate) and poiy(1,1- dihydroperfluorooctyl methacryiate).
  • Graft copolymers may be also be used and include, for example, poly(styrene-g-dimethylsiloxane), poly(methyl acrylate-g- 1,1'dihydroperfluorooctyl methacryiate), and poly(1 ,1 '-dihydroperfluorooctyl acrylate-g-styrene). Random copolymers may be employed and examples of such include, but are not limited to, copolymers or terpolymers of tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, and ethylene. Other examples can be found in I. Piirma, Polymeric Surfactants (Marcel Dekker 1992); and G. Odian,
  • non-polymeric molecules may be used such as perfluoro octanoic acid, surfynols, perfluoro(2-propoxy propanoic) acid, fluorinated alcohols and diols, along with various fluorinated acids, ethoxylates, amides, glycosides, alkanolamides, quaternary ammonium salts, amine oxides, and amines. Mixtures of any of the above may be used.
  • nonionic surfactants optionally can be used in the invention.
  • nonionic surfactants that can be used include, without limitation, those which are from the family of alkylphenoxypoly(ethyleneoxy)ethanols.
  • anionic surfactants that may be employed include, but are not limited to, those that are selected from the broad class of sulfonates, sulfates, ethersulfates, sulfosuccinates, diphenyloxide disulfonates, and the like, as well as others that are apparent to one skilled in the art.
  • Cationic surfactants that can be used are numerous and include, without limitation, those which employ cationic moieties include quaternary ammonium, protonated ammonium, sulfonium, and phosphonium moieties.
  • the surfactants can be used in conjunction with the salt having the CO -philic segment and co-solvent such that micelles are formed which are rich in co-solvent and salt in a homogeneous carbon dioxide-rich phase.
  • the compositioi of matter in such an embodiment comprises from about 0.001 , 0.005, 0.01 , or 0.02 to about 0.06, 0.08, or 0.1 percent by weight of surfactant.
  • the surfactants may be used to form bicontinuous co-solvent- rich and carbon dioxide-rich phases, with the predominant ionic pathway believed to be occurring in the co-solvent-rich phase.
  • the term "bicontinuous phase" may be defined as a sample- spanning, intertwined arrangement of a co-solvent rich phase and a carbon dioxide rich phase stabilized by surfactant regions, i.e., an emulsion (e.g., microemulsion) which is continuous in the two phase system.
  • the composition preferably comprises from about 0.001. 0.005, 0.01, or 0.02 to about 0.06, 0.08, or 0.1 percent by weight of surfactant.
  • preferred surfactants include, without limitation, those listed herein (e.g., fluorinated surfactants). Particularly preferred surfactants include perfluoropolyether carboxylates such as those derived from the fluoroalkylene oxide class. Various amounts of surfactant may be used for the purposes of the invention. Preferably, the composition of matter comprises from about 0.001. 0.005, 0.01 , or 0.02 to about 0.06, 0.08, or 0.1 percent by weight of surfactant.
  • the composition of matter preferably has an ionic conductivity which ranges from about 10 "6 , 10 '5 , or 10 "4 S/cm to about 10 "3 , 10 '2 , or 10 '1 S/cm.
  • The. composition of matter preferably displays increased ionic conductivity relative to a composition of matter that does not employ a salt that includes a C ⁇ 2 -philic segment.
  • the invention provides a process which utilizes the composition of matter as defined herein.
  • Such processes include those which encompass electrochemical aspects.
  • Exemplary processes include, without limitation, an electroorganic synthesis, a waste destruction, a separation, a surface modification, an electrodeposition, an electrodissolution, and an in- situ generation of initiator.
  • the invention in another aspect, relates to a method of increasing the ionic conductivity of a carbon dioxide-containing fluid.
  • the method comprises introducing a salt into the carbon dioxide-containing fluid such that the - salt dissolves therein and increases the ionic conductivity of the carbon dioxide-containing fluid.
  • the salt is comprises at least one CO 2 -philic segment.
  • the method of the invention may encompass, but is not limited tb, any of embodiments set forth hereinabove.
  • the invention may be carried out in various high pressure cells or vessels, including those which are batch, semi-continuous, or continuous.
  • the cell or vessel may optionally be subject to mechanical agitation by employing appropriate devices (e.g., a paddle stirrer or impeller stirrer).
  • the cell or vessel may use appropriate heating devices (e.g., a heating furnace or heating rods).
  • bone-dry carbon dioxide National Welders of Raleigh, NC, 99.8 percent, 860 psia
  • HPLC grade methanol (Fischer Scientific of Atlanta, Georgia) was used as a co-solvent.
  • the ionic compounds that were studied include lithium trifluoroacetate (95 percent), sodium trifluoroacetate (98 percent), and potassium trifluoroacetate (98 percent) all supplied by the Aldrich Chemical Company of Milwaukee, Wisconsin.
  • lithium acetate (99.9 percent) furnished by Sigma of Milwaukee, Wisconsin was used.
  • a 1 M solution of each salt in methanol was used as stock solution.
  • salt weighing was conducted in an argon-filled glove box. The solution was kept in a septum-sealed bottle to minimize humidity infiltration. Water content of the methanol + salt solutions varied between 150 ppm and 1000 ppm, as measured by Karl-Fisher titration. The measurements were believed to depend on the salt concentration. - " '
  • FIG. 1A is a schematic of the apparatus used in the experiments. Carbon dioxide is pumped into the cell using a manually operated pressure generator (model 62-1-10 made available from the High Pressure Equipment Co. of Erie, Pennsylvania.
  • a cylindrical high-pressure vessel was constructed from 316 stainless steel (see FIG. 2). The vessel has five taper-sealed ports on the cylindrical surface, and threaded fixtures on the flat surfaces.
  • the electrodes were mounted on a 316 stainless steel plug using insulated electrical feedthroughs (see FIG. 1B), and the plug was held against a teflon gasket by a threaded thrust ring.
  • a sapphire window (1-inchdiameter, 3/8-inch thickness, I NSACO) was secured to the opposite face of the vessel by a threaded retainer and a Teflon seal.
  • the volume of electrolyte within the cell was 22 ⁇ 0.5 cm 3 .
  • Heating tape (Omega of Stamford, Connecticut) was wrapped around the vessel and the temperature was controlled using a thermocouple (T-type) positioned in front of the platinum (Pt) flag and a temperature controller (Omega, CN 76000 series).
  • the five 1/ 6-inch diameter taper- sealed ports were used for sample injection, thermocouple, fluid inlet/outlet, pressure gauge (Omega, PX 615 series with DP 25 series meter), and rupture disk.
  • Pt flag electrodes (5 x 5 mm 2 ) were spot welded to a Pt wire (0.02-inch diameter) that served as the electrical lead.
  • the Pt wire was threaded through teflon tubing which, in turn, was placed in a 1/16 stainless steel tube that was put through the stainless steel plug and fixed in place by a taper seal (FIG. 1B and FIG. 2).
  • Each electrode was sealed at the wetted end by Torr Seal® made available by Varian of Palo Alto, California, and when assembled the working and counter electrodes were approximately parallel and positioned 1 cm apart.
  • the cell constant for conductivity calculations was measured as 1.53 cm using a KCI standard solution. Impedance measurements were made with a BAS Zahner IM6e Impedance Analyzer. Most of the measurements were performed in a frequency range of 500 mHz to 1MHz and a 200 mV to 1000 mV amplitude.
  • the cell was filled with CO 2 prior to loading at approximately 800 psig and vented to atmospheric pressure three times. Thereafter, 5 mL of the salt + methanol stock solution was injected into the cell through a syringe, and the injection port was plugged. Carbon dioxide was added to the cell so that an "initial-fill condition" of 17 ⁇ 1 °C and 760 ⁇ 20 psig was obtained. After heating to the desired temperature, the pressure was increased by adding carbon dioxide through the pump while keeping the temperature constant. Sufficient time was allowed to reach equilibrium before recording a measurement. At the conclusion of each measurement, the mixture was vented, the cell was cooled to room temperature, rinsed with methanol several times, and heated to 100°C for 30 minutes while continuously purging with CO 2 . The clean and dried cell was stored open to the atmosphere until used in the next set of experiments.
  • Example 2 The procedure according to Example 1 was repeated except that NaCF 3 CO2 was investigated. The results are illustrated in FIG. 3B.
  • KCF3CO 2 was investigated. The results are illustrated in FIG. 3C.
  • Example 7 The procedure according to Example 4 was repeated except that KCF 3 CO 2 was investigated. The results are illustrated in FIG. 4C.
  • FIGS. 6A and 6B illustrate the conductivity results for mixtures containing 0.5 mmol of salt at various temperatures and pressures. In general, the lithium salt displayed the highest conductivity.
  • FIGS.7A and 7B illustrate the conductivity results for mixtures containing 0.05 mmol of salt at various temperatures and pressures. In general, the lithium salt displayed the highest conductivity.
  • FIG. 8 illustrate the conductivity results for the salts illustrated in
  • the lithium salt having a concentration of 0.05 mmol displayed the highest conductivity range.
  • the 0.05 mmol concentration is believed to display a higher conductivity relative to the

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Abstract

L'invention porte sur une composition de substance comprenant un composé ionique et un fluide contenant du dioxyde de carbone composé d'au moins un sel dissout dans ce fluide avec un ou plusieurs segments CO2-phile. Ledit fluide contenant du dioxyde de carbone présente une conductivité ionique plus élevée par rapport à un tel fluide dépourvu en sel.
PCT/US2001/045574 2000-11-03 2001-10-24 Methodes permettant d'ameliorer la conductivite ionique dans le dioxyde carbone et ses melanges WO2002036859A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6010542A (en) * 1997-08-29 2000-01-04 Micell Technologies, Inc. Method of dyeing substrates in carbon dioxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6010542A (en) * 1997-08-29 2000-01-04 Micell Technologies, Inc. Method of dyeing substrates in carbon dioxide

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