Polyalkylamine complexes for ligand extraction and generation

• US 4,959,135 A
• Filed: 02/03/1989
• Issued: 09/25/1990
• Est. Priority Date: 02/25/1987
• Status: Expired due to Term

• Current Assignee: W R Grace & Company - CONN (Standard Industries Holdings, Inc.)
• Original Assignee: Aquanautics Corporation
• Inventors: De Castro, Emory S., Deardurff, Larrie A., Zenner, Bruce D., Kerr, John B., Ciccone, Joseph P.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): GORGOS, KATHRYN L
• Application Number:
  US07/306,730
• Time in Patent Office: 599 Days
• Field of Search: 204/129, 204/130, 204/180.1, 204/182.3, 204/182.5, 204/233, 204/235, 252/188.28, 261/101, 261/DIG. 28, 422/48, 423/219, 423/605, 423/579, 423/632, 55/16, 55/37, 55/58, 55/59, 546/2, 546/10, 546/11, 546/12, 548/101, 548/108, 548/109, 548/402, 556/13, 556/14, 556/42, 556/44, 556/45, 556/49, 556/50, 556/51, 556/57, 556/110, 556/113, 556/114, 556/136, 556/137, 556/138, 556/146, 556/148, 544/4
• US Class Current: 205/633
• CPC Class Codes: C01B 13/0244 by complexation
• CPC Class Codes: C01B 2210/0046 Nitrogen
• CPC Class Codes: C02F 1/20 by degassing, i.e. liberation of dissolved gases degasification of liquids in general B01D19/00; arrangement of degassing apparatus in boiler feed supply F22D
• CPC Class Codes: C07F 15/065 without a metal-carbon linkage

Abstract

Methods and apparatus for the extraction of a ligand such as molecular oxygen from a first fluid environment and for release of a ligand such as molecular oxygen, as well as ligand carrier compounds therefor comprising linear, pentadentate polyalkylamines and transition metal ions. The carrier compounds have the general formula: ##STR1## where, each of R₁ and R₂ is independently an organic group including a sulfur, an oxygen or a nitrogen coordinated to M;

each of m, n, o, and p is 1, 2, 3, or 4;

X is selected from the group consisting of 2,6-pyridyl, 2,6-piperidyl, 2,5-pyrrolyl, 2,4-imidazolyl, substituted heterocyclic amines, --)--, --S--, ##STR2## and ##STR3## where R₃ is hydrogen, lower alkyl or aralkyl; and M is a transition metal ion.

Claims

1. A metallic complex of a polyalkylamine of the general formula ##STR10## where, R₁ =R₂ =2-pyridyl;

o=2, 3, or 4;

R₃ is hydrogen for o=2 or 4;

R₃ is methyl for o=3; and

M is a transition metal ion.

2. A metallic complex of a polyalkylamine of the general formula ##STR11## where, each of R₁ and R₂ is independently selected from the group consisting of 2-pyridyl and amino;

each of m, n, o, and p is independently 1, 2, 3, or 4;

X is 2,6-pyridyl; and

M is a transition metal ion;

wherein at least two of m, n, o, and p are unequal.

3. A metallic complex of a polyalkylamine of the general formula ##STR12## where, each of R₁ and R₂ is independently an organic group including a nitrogen coordinated to M;

each of m, n, o, and p is independently 1, 2, 3, or 4;

X is selected from the group consisting of 2,6-pyridyl, substituted 2,6-pyridyl, 2,4-imidazolyl, substituted 2,4-imidazolyl and >

N-H; and

M is transition metal ion; and

wherein n and o are unequal.

4. The metallic complex according to claim 3 wherein R₁ and R₂ is each independently selected from the group consisting of amino, alkylamino, dialkylamino, 2-pyridyl substituted 2-pyridyl, 2-imidazolyl, 4-imidazolyl, substituted 2-imidazolyl, and substituted 4-imidazolyl.

5. The metallic complex according to claim 3 wherein R₁ and R₂ is each independently selected from the group consisting of amino, 2-pyridyl, 2-imidazolyl, and 4-imidazolyl.

6. The metallic complex according to claim 3 wherein M is selected from the group consisting of manganese, iron, cobalt, copper, ruthenium, rhodium, and vanadium.

7. The metallic complex according to claim 3 wherein M is selected from the group consisting of manganese, iron, and cobalt.

8. The metallic complex according to claim 3 wherein X is 2,6-pyridyl or ##STR13##

9. A composition of matter for use in electrochemical ligand extraction and generation processes comprising:

an aqueous solution of greater than about 10 millimoles per liter of a metallic complex of a polyalkylamine having the general formula;

##STR14## where, each of R₁ and R₂ is independently an organic group including a nitrogen atom coordinated to M;

each of m, n, o, and p is independently 1, 2, 3, or 4;

X is selected from the group consisting of 2,6-pyridyl, substituted 2,6-pyridyl 2,4-imidazolyl, substituted 2,4-imidazolyl, and;

##STR15## and M is a transition metal ion.

10. The composition of matter according to claim 9 wherein M is selected from the group consisting of manganese, iron, cobalt, copper, ruthenium, rhodium, and vanadium.

11. The composition of matter according to claim 9 wherein M is selected from the group consisting of manganese, iron, and cobalt.

12. The composition of matter according to claim 9 wherein R₁ and R₂ is each selected from the group consisting of amino, alkylamino, dialkylamino, 2-pyridyl, substituted 2-pyridyl, 2-imidazolyl, 4-imidazolyl, substituted 2-imidazolyl, and substituted 4-imidazolyl.

13. The composition of matter according to claim 9 wherein R₁ and R₂ is each selected from the group consisting of amino, 2-pyridyl, 2-imidazolyl, and 4-imidazolyl.

14. The composition of matter according to claim 9 wherein X is 2,6-pyridyl, or ##STR16##

15. The composition of matter according to claim 9 further comprising a supporting electrolyte.

16. The composition of matter according to claim 15 wherein the supporting electrolyte is a salt selected from the group consisting of sodium chloride, and potassium chloride.

17. The composition of matter according to claim 15 wherein the supporting electrolyte is a salt having a concentration between about 0.1 and about 1.0 molar.

18. The composition of matter according to claim 9 wherein the aqueous solution has a pH of between about 3 and about 12.

19. The composition of matter according to claim 9, titrated to a pH of about 1 pH unit above the pH at which greater than about 50% of the metallic complex, when exposed to an oxygen containing environment, is present as an oxygen complex.

20. A method for extracting a ligand from a first fluid environment, the method comprising the steps of:

contacting the first fluid environment containing ligand with a first surface of a first ligand-permeable membrane having a first surface and a second surface wherein the membrane separates the environment from an interior space of a container;

contacting an aqueous carrier fluid with the second surface of the membrane wherein the carrier fluid is confined in the container and the carrier fluid contains a carrier compound, whereby at least a portion of a ligand which diffuses through the membrane binds to the carrier compound to give bound ligand complex;

transporting the carrier fluid containing the bound ligand complex to a first electrode compartment of an electrochemical cell which forms a second portion of the container;

electrochemically modulating the carrier compound to an oxidation state having relatively less binding affinity for ligand, thereby releasing free ligand into the carrier fluid and producing a non-binding state carrier compound;

removing ligand from the carrier fluid to give a ligand depleted carrier fluid;

transporting the ligand depleted carrier fluid containing the non-binding state carrier compound to a second electrode compartment of an electrochemical cell which forms a third portion of the container; and

electrochemically modifying the non-binding state carrier compound to reform the binding state carrier compound;

wherein, the carrier compound comprises a metallic complex of a polyalkylamine having the general formula;

##STR17## where, each of R₁ and R₂ is independently an organic group including a nitrogen atom coordinated to M;

each of m, n, o, and p is independently 1, 2, 3, or 4;

X is selected from the group consisting of 2,6-pyridyl, substituted 2,6-pyridyl, 2,4-imidazolyl, substituted 2,4-imidazolyl and;

##STR18## and M is a transition metal ion.

21. The method of claim 20 further comprising the step of transporting the carrier fluid containing the non-binding state carrier compound and free ligand to a fourth portion of the container in which ligand is removed from the carrier fluid to yield the ligand-depleted carrier fluid.

22. The method of claim 21 wherein the ligand removing step comprises contacting the carrier fluid with a second ligand-permeable membrane which separates the carrier fluid from a second fluid environment.

23. The method of claim 20 wherein the ligand comprises molecular oxygen.

24. The method of claim 20 wherein the carrier fluid comprises primarily water and includes, in addition to the carrier compound. a supporting electrolyte and is buffered to a selected pH.

25. A method for extracting a ligand from a first fluid environment and releasing the ligand to a second fluid environment, the method comprising the steps of:

providing an electrochemical cell including an anode, a cathode and an electrolyte comprising a transition metal carrier compound having the general formula;

##STR19## where, each of R₁ and R₂ is independently an organic group including a nitrogen atom coordinated to M;

each of m, n, o, and p is independently 1, 2, 3, or 4;

X is selected from the group consisting of 2,6-pyrdiyl, substituted 2,6-pyridyl, 2,4-imidazolyl, substituted 2,4-imidazolyl, and;

##STR20## and M is a transition metal ion;

providing a potential across the cell sufficient to convert the transition metal ion of the carrier compound to a binding valance state at the cathode and convert, at the anode, the transition metal ion of the carrier compound ligand complex to a non-binding valence state;

communicating the ligand from the first fluid environment to the electrolyte at the cathode so that the carrier compound ligand complex is formed between the ligand and the binding valence state carrier compound;

transporting the carrier compound ligand complex to the anode for release of the ligand; and

electrochemically releasing the ligand from the carrier compound ligand complex to the second fluid environment.