EP0476115A1 - Verfahren zur abtrennung von sauerstoff aus einer gasmischung - Google Patents

Verfahren zur abtrennung von sauerstoff aus einer gasmischung

Info

Publication number
EP0476115A1
EP0476115A1 EP91907588A EP91907588A EP0476115A1 EP 0476115 A1 EP0476115 A1 EP 0476115A1 EP 91907588 A EP91907588 A EP 91907588A EP 91907588 A EP91907588 A EP 91907588A EP 0476115 A1 EP0476115 A1 EP 0476115A1
Authority
EP
European Patent Office
Prior art keywords
complex
dioxygen
metal
oxidation
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP91907588A
Other languages
English (en)
French (fr)
Inventor
Christian Amatore
Said Aziz
Anny Jutand
François Draskovic
Kenneth Yamaguchi
Panayotis Cocolios
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0476115A1 publication Critical patent/EP0476115A1/de
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0233—Chemical processing only
    • C01B13/0244—Chemical processing only by complexation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0285—Physical processing only by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0051—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0078—Noble gases
    • C01B2210/0082—Argon

Definitions

  • the subject of the invention is the use of transition metal complexes for the separation of dioxygen from a mixture of gases containing it.
  • the first three consist of a non-destructive fixation of the O 2 molecule on the metal and are therefore likely to intervene in the processes of separation of the oxygen molecule from a gaseous mixture.
  • the most complex families of complexing agents used in this regard include cobalt linked to a Schiff base, an amino acid, a porphyrin, a polyalkyamine or a polyalkylamino acid, or also iron linked to a cryptand or to a porphyrin.
  • Other families include, as transition metal, manganese or copper linked respectively to one or more phosphines or to a protein.
  • spin for example: Co II low spin - Co II high spin (function of the field strength of the ligand used), of complexation of oxygen, and of dimerization of the oxygen complex.
  • L represents a coordination site belonging to one or more inorganic or organic ligand (s), mono or polydentate (s) identical or different, said ligands being capable of stabilizing the low valences of M, chosen in particular among the following ligands: . carbon monoxide
  • M is a transition metal capable of fixing O 2 by forming dihapto dioxygenated peroxide compounds
  • X is an organic coordinating anion, for example a carboxylate ion, or an inorganic anion, for example a halide and in particular a chloride ion,
  • * p represents the degree of oxidation of M in the complex of formula (A),
  • * m, equal to 1 or 2 represents the number of metal centers of the complex
  • n ', m', x ' have the same meanings as n, m, x respectively with: 2 ⁇ n' ⁇ n, 1 ⁇ m' ⁇ m, 0 ⁇ x' ⁇ x.
  • a group of metal complexes usable in the invention is illustrated by the formula (C), [L n M + p ] + p , in which the symbols have the meanings given above.
  • the metal M is coordinated, in addition to the ligands comprising L coordinating sites, to anions so as to at least partially block the unoccupied coordination sites of M.
  • the invention also relates to dinuclear complexes corresponding to the formula:
  • L, M, X, n, p, z, and x are as defined above, where the dinuclear structure is provided either by bridging X - z anions, or by polydentate chelating ligands carrying at least two coordinating sites L, either by a metal-metal bond, or by a combination of these bonds.
  • the metal complexes which can be used in the invention can be in the state of anions or cations. They are then associated with one or more against mineral or organic non-coordinating ion (s) which counterbalances their charge.
  • These ions come from the support electrolyte and can in particular be quaternary ammonium salts, quaternary phosphonium salts, alkali or alkaline-earth complexed or not or the like, for cations, and halide ions, tetrafluoroborates, hexafluorophosphates, sulfates, carbonates, phosphates or the like, for anions.
  • the dioxygenated complexes of formula (B) result from the fixation of dioxygen by the compounds of formula (A) and more particularly by the compounds of formula (C), (D) or (E).
  • Compounds (A), (C), (D) and (E) can be synthesized beforehand or they can be formed in situ from commercial products or not.
  • Metal salts at varying degrees of oxidation, can serve as precursors to the active species, such as the halogen, acetate, nitrates, sulfates, fluoroborates, perchlorates or the like salts.
  • Compounds which are particularly suitable for the process in the case where M represents Pd include PdCl 2 and Na 2 PdCl 4 .
  • Ligands which are particularly suitable for the preparation of the complexes of the invention are chosen from phosphines. Mention will in particular be made of triphenylphosphines, alkyl-, aryl- or alkylarylphosphines, mono- or bidentates and in particular triphenylphosphine and tri-n-butylphosphine.
  • sulfonated phosphines such as the trisulfonated triphenylphosphine P (C 6 H 4 SO 3 H) 3 or disulfonated P (C 6 H 5 ) (C 6 H 4 SO 3 H) 2 or monosulfonated P (C 6 H 5 ) 2 (C 6 H 4 SO 3 H).
  • Phosphine oxides and phosphites are also suitable when operating in an aqueous medium.
  • Metal complexes particularly preferred for the implementation of the invention contain as transition metal M palladium, platinum, nickel or rhodium.
  • the electrochemical oxidation step is carried out in the compar anode cell of an electrolysis cell.
  • Suitable electrolytes are of the perfluoroborate or tetraphenylborate or perfluorophosphate or halide or sulphate or carbonate or carbonate or phosphate of alkali or alkaline earth, complexed or not, of quaternary ammonium salt, of phosphonium and include, for example, tetrafluoroborate of tetra-n- butyl ammonium or triethylbenzylammonium hexafluorophosphate.
  • the operation is carried out at a potential chosen as a function of the oxygenated metal complex to be oxidized and the composition of the medium.
  • the oxidation stage is followed by the desorption of the oxygen which is also carried out in the anode compartment of the electrolysis cell, the separation of the oxygen from the solution being carried out by means of a gas-liquid separation tower placed in downstream of the anode compartment.
  • the solution obtained is transferred at the outlet of the previous tower, into the cathode compartment of the electrolysis cell, where the electrochemical reduction is carried out at a more negative potential than that used in the oxidation step, which leads to a lower valence complex, capable of fixing the oxygen again in an absorption tower placed between the exit of the cathode compartment and the entry of the anode compartment, the electrochemical oxidation-reduction cycle then being resumed.
  • the oxygen absorption step is carried out by contacting the gas mixture with the metal complex in reduced form in solution.
  • the active species (A) is formed in situ.
  • a mixture of metal halide, for example PdCl 2 or Na 2 PdCl 4 , and of ligand, for example triphenylphosphine or tri-n-butylphosphine, which is rapidly introduced into a species (G), is introduced into the cathode compartment.
  • ligand for example triphenylphosphine or tri-n-butylphosphine
  • an advantageous variant of the process consists in reacting this superoxide ion generated in the cathode compartment on the species (G ) to lead directly to the dioxygenated complex (B).
  • the species (G) is the complex (R 3 P) 2 PdCl 2 this reaction is written
  • the materialization of this transformation can advantageously be carried out by the use of an electrochemical cell under pressure, or the use of a porous cathode with gas diffusion.
  • the porous cathode also has the following two advantages:
  • a solution of the complex is used in an organic solvent.
  • a solvent preferably having a low ohmic drop is preferably chosen.
  • Suitable solvents of this type include dimethylformamide, dimethylsulfoxide, acetonitrile, or even benzonitrile, dichloromethane, tetrahydrofuran.
  • the operation is carried out in an aqueous medium, the ligands used being then chosen from water-soluble ligands.
  • the separation of dioxygen is carried out at atmospheric pressure.
  • the complex solution is then brought into contact with compressed air.
  • the absorption of oxygen is carried out at atmospheric pressure and the liquid is compressed using a pump to the desired pressure.
  • This process makes it possible to separate the oxygen from the air, in particular in a continuous process.
  • Figures 1 to 4 represent voltamograms referring to selected examples:
  • FIG. 1 relates to the electrochemistry of the L 4 Pd ° complex in which L represents triphenylphosphine.
  • the curve LA is the voltamogram of the complex (PPh 3 ) 4 Pd ° under an argon atmosphere; curve 1B that of the same complex after introduction of oxygen; curve 1C represents the voltamogram of (PPh 3 ) 4 Pd ° in the presence of an excess of O 2 and the curve 1D results from the previous one after addition of two equivalents of nBu 4 N + Cl- with respect to the starting complex.
  • Figures 2 and 3 show the voltamograms of the complex (PPh 3 ) 2 PdO 2 obtained chemically, then dissolved in dimethylformamide. More particularly, Figure 2 reproduces the voltammograms obtained with an initial cathode scan for the complex (PPh 3 ) 2 PdO 2 alone (curve 2A) and added with two equivalents of nBu 4 N + Cl- (curve 2B).
  • FIG. 4 shows the voltamograms recorded for the complex (PPh 3 ) 2 PdO 2 prepared in situ in dimethylformamide from PdCl 2 and PPh 3 . More specifically, curves 4A to 4D represent:
  • EXAMPLE 1 EISCTROCHIHICAL STUDY OF THE METAL COMPLEX L 4 Pdo IN WHICH THE METAL IS COORDINATED BY FOUR LIGANDS HONODENTATES TRIPHENYLPHOSPHINE PPh 3 .
  • the oxidation-reduction potential studies were carried out in dimethylformamide (DMF) or dichloromethane (CH 2 Cl 2 ) in the presence of 0.3 M tetra-n-butylammonium tetrafluoroborate (nBu 4 NBF 4 ) as the electrolyte Support .
  • the L 4 Pd ° concentration is 2mM.
  • the potentials were measured with respect to the saturated calomel electrode (DHW), and determined by cyclic voltammetry on the gold (Au) or carbon (C) electrode, at the scanning speeds of 200 and 100 mV.s - 1 respectively.
  • DHW saturated calomel electrode
  • Au gold
  • C carbon
  • the L 4 Pd ° complex leads to the dioxygen compound L 2 Pd II O 2 , according to:
  • the reduced species is able to fix dioxygen again and gives rise to the same oxidation reaction as above with 2 electrons around + 0.50V. This species is much more hungry for dioxygen than its precursor L 4 Pdo.
  • L 2 Pd 2 O 2 The oxidation of L 2 Pd 2 O 2 involves two electrons per mole. It releases molecular oxygen and leads to the L 2 PdCl 2 complex, according to:
  • composition of the medium solvent, dimethylformamide, 70 ml; L 2 PdO 2 5mM; benzyltri-n-butyl ammonium chloride, 11mM; support electrolyte, tetra-n-butylammonium hexafluorophosphate, 0.3M, medium saturated with oxygen.
  • EXAMPLE 5 ELECTROCHEMISTRY OF THE L 2 PdO 2 COMPLEX PREPARED IN SITU FROM PdCl 2 AND TRIPHENYLPHOSPHINE, PPh 3 .
  • the species oxidized to + 0.22V does not come from that reduced to - 2.17V, but from the species which results from the reaction of dioxygen with [L 2 Pd ° Cl x ] -x ( reversal of the return sweep at -1.5 V or of the reaction of the superoxide ion O 2 - with the L 2 Pd II Cl 2 complex, (in the case of a sweep back to
  • the recorded voltammogram shows on the side of the reduction a wave at -0.94V attributed to the reduction in dioxygen and a second wave at -1.39V attributed to the reduction in L 2 Pd II Cl 2 .
  • the disappearance of the wave of [L 2 PdoCl x ] -x and the appearance of the wave of oxidation of [L 2 PdO 2 Cl x ] -x at + 0.22V are observed.
  • An oxidation wave at + 0.79V is attributed to the oxidation of chloride ions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP91907588A 1990-03-27 1991-03-19 Verfahren zur abtrennung von sauerstoff aus einer gasmischung Ceased EP0476115A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9003886A FR2660210B1 (fr) 1990-03-27 1990-03-27 Procede d'utilisation de complexes de metaux de transition pour la separation du dioxygene d'un melange de gaz par electrodecomplexation.
FR9003886 1990-03-27

Publications (1)

Publication Number Publication Date
EP0476115A1 true EP0476115A1 (de) 1992-03-25

Family

ID=9395154

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91907588A Ceased EP0476115A1 (de) 1990-03-27 1991-03-19 Verfahren zur abtrennung von sauerstoff aus einer gasmischung

Country Status (13)

Country Link
US (1) US5296105A (de)
EP (1) EP0476115A1 (de)
JP (1) JPH04506627A (de)
AU (1) AU632232B2 (de)
BR (1) BR9105169A (de)
CA (1) CA2056410A1 (de)
CS (1) CS80591A2 (de)
FR (1) FR2660210B1 (de)
HU (1) HU913557D0 (de)
PL (1) PL293018A1 (de)
PT (1) PT97183A (de)
WO (1) WO1991014649A1 (de)
ZA (1) ZA912276B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5871565A (en) * 1997-01-15 1999-02-16 Praxair Technology, Inc. Vacuum/pressure swing adsorption (VPSA) for production of an oxygen enriched gas
US8268048B2 (en) * 2008-10-14 2012-09-18 University Of Kansas Oxygen binding of nanoparticulate metal complexes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4457898A (en) * 1982-04-30 1984-07-03 Facilitated Separations, Ltd. Managanese compounds and sorption of gases using manganese compounds
US4475994A (en) * 1983-12-27 1984-10-09 Maxdem Incorporated Method and apparatus for separating oxygen from a gaseous mixture
US4680037A (en) * 1986-08-28 1987-07-14 Air Products And Chemicals, Inc. Lacunar cobalt complexes for oxygen separation
WO1988002036A1 (en) * 1986-09-22 1988-03-24 Sri International Gas separation process
US4952289A (en) * 1988-05-09 1990-08-28 Aquanautics Corporation Macrocyclic amine complexes for ligand extraction and generation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9114649A1 *

Also Published As

Publication number Publication date
CS80591A2 (en) 1991-09-15
AU7665391A (en) 1991-10-21
JPH04506627A (ja) 1992-11-19
FR2660210A1 (fr) 1991-10-04
AU632232B2 (en) 1992-12-17
CA2056410A1 (fr) 1991-09-28
HU913557D0 (en) 1992-07-28
PT97183A (pt) 1991-11-29
FR2660210B1 (fr) 1992-06-05
WO1991014649A1 (fr) 1991-10-03
PL293018A1 (en) 1992-10-05
US5296105A (en) 1994-03-22
BR9105169A (pt) 1992-05-19
ZA912276B (en) 1991-12-24

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