IP Library Granted Patent US 11,731,117
Granted Patent B2
US 11,731,117 · App. 16/886,418 · Granted Aug 22, 2023

Compositions of certain manganese accumulating plants

Inventors: Claude Grison (Castelnau le Lez, FR); Vincent Escande (Montpellier, FR)
Assignees: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITÄ{umlaut over (C)}Ü{umlaut over ( )}Ë DE MONTPELLIER
B01J31/2295B01J23/34B01J23/8892B01J37/009B01J37/0036B01J37/0072B01J37/06B01J37/082B01J37/14B01J37/30B01J37/346B01J37/36B09C1/10C07C1/20C07C5/367C07C45/29C07C49/807C07C67/307C07C211/50C07C245/08C07D213/80C07D307/30C07D307/68C07D401/04C07D403/14C07D407/04B01J2231/005B01J2531/72
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Quick Facts
Patent No.
US 11,731,117
App. No.
16/886,418
Granted
Aug 22, 2023
Kind
B2
Abstract

Compositions of manganese accumulating plants.

Claims (42)

1. Composition comprising at least a metallic or a polymetallic agent containing less than 10% by weight of organic matter and comprising manganese having a degree of oxidation (II) (Mn (II)), a degree of oxidation (III) (Mn (III)) or a degree of oxidation (IV) (Mn (IV)), and optionally a metal or several metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al), wherein the manganese content is between 15,000 and 270,000 ppm, and wherein said composition is obtained by carrying out a method comprising the following steps:

a) Dehydrating a plant or a part of a plant, said plant or said part of said plant belonging to a genus selected from the group consisting of Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Helanthius, Macadamia, Maytenus, Pinus, Phytolacca, Spermacone, Stenocarpus, Virotia and Grevillea , that has accumulated manganese (Mn), and optionally a metal or several metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminium (Al),

b) Grinding the dried plant or dried part of plant obtained from step a), and obtaining a grinded mixture,

c) Thermally treating the grinded mixture obtained from step b), and obtaining an ash.

2. Composition according to claim 1 comprising at least manganese (Mn) in the form Mn (II) in a quantity above 25,000 ppm, and at least one metal selected from the group consisting of calcium (Ca), magnesium (Mg), iron (Fe) or aluminium Al(III), at least manganese and/or at least one of said metals being in the form of chloride or of sulphate or in the form of a complex with a chloride of another metal, and cellulosic degradation fragments, and/or glucose degradation products and less than about 2%.

3. Composition according to claim 1 containing at least one metallic or polymetallic agent comprising manganese (Mn) in the form Mn (III) or Mn (IV) and optionally one or more metals selected from calcium (Ca), magnesium (Mg), iron (Fe) or aluminium Al(III) said agent comprising at least one of said metals in the form of salts, oxide, chelate or complex with a chloride of another metal.

4. Composition according to claim 1 , wherein the method further comprises a step d) of treatment of the ash obtained from step c) with an acid, and obtaining a solution or a suspension, followed by dehydration of the solution or suspension obtained so as to obtain a dry residue.

5. Composition according to claim 4 , wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid, sulphuric acid, acetic acid, trifluoromethanesulphonic acid, nitric acid, perchloric acid, phosphoric acid, trifluoroacetic acid and para-toluenesulphonic acid.

6. Composition according to claim 4 , wherein the method further comprises:

a step e) of removal of the insoluble matter of the suspension obtained from step d) by filtration on an inert mineral solid or by centrifugation, a step that is followed by dehydration of the solution obtained so as to obtain a dry residue, or

a step f) of complete or partial purification of the solution obtained from step d) on ion-exchange resins followed by dehydration of the solution obtained so as to obtain a dry residue.

7. Composition according to claim 1 , wherein the method further comprises:

a step g) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the ash obtained from step c) to manganese with a degree of oxidation (III) (Mn (III)) by subjected said ash

either to the action of dioxygen of the air in the presence of OH − ions and then to a treatment with an anhydride,

or to the action of pyrrole in the presence of an aldehyde in order to obtain the formation of a porphinato-manganese complex with a degree of oxidation (II), which is subjected to the action of dioxygen of the air,

and the product obtained from said conversion is subjected to dehydration in order to obtain a dry residue comprising manganese with a degree of oxidation (III) (Mn (III)), or

a step h) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the ash obtained from step c) to manganese with a degree of oxidation (IV) (Mn (IV)) by subjected said ash to the action of dioxygen of the air in the presence of OH − ions and the suspension obtained is subjected to an acid treatment and then to dehydration so as to obtain a reagent practically devoid of manganese in the form Mn 2 O 4 or Mn 2 O 3 [<3%] comprising manganese with a degree of oxidation (IV) (Mn (IV)).

8. Composition according to claim 4 , wherein the method further comprises

a step g) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the dry residue obtained from step d) to manganese with a degree of oxidation (III) (Mn (III)) by subjected said dry residue

either to the action of dioxygen of the air in the presence of OH-ions and then to a treatment with an anhydride,

or to the action of pyrrole in the presence of an aldehyde in order to obtain the formation of a porphinato-manganese complex with a degree of oxidation (II), which is subjected to the action of dioxygen of the air,

and the product obtained from said conversion is subjected to dehydration in order to obtain a dry residue comprising manganese with a degree of oxidation (III) (Mn (III)), or

a step h) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the dry residue obtained from step d) to manganese with a degree of oxidation (IV) (Mn (IV)) by subjected said dry residue to the action of dioxygen of the air in the presence of OH − ions and the suspension obtained is subjected to an acid treatment and then to dehydration so as to obtain a reagent practically devoid of manganese in the form Mn 2 O 4 or Mn 2 O 3 [<3%] comprising manganese with a degree of oxidation (IV) (Mn (IV)).

9. Composition according to claim 6 , wherein the method further comprises:

a step g) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the dry residue obtained from step e) or step f) to manganese with a degree of oxidation (III) (Mn (III)) by subjected said dry residue

either to the action of dioxygen of the air in the presence of OH-ions and then to a treatment with an anhydride,

or to the action of pyrrole in the presence of an aldehyde in order to obtain the formation of a porphinato-manganese complex with a degree of oxidation (II), which is subjected to the action of dioxygen of the air,

and the product obtained from said conversion is subjected to dehydration n order to obtain a dry residue comprising manganese with a degree of oxidation (III) (Mn (III)), or

a step h) of conversion of the manganese with a degree of oxidation (II) (Mn (II)) of the dry residue obtained from step e) or step f) to manganese with a degree of oxidation (IV) (Mn (IV)) by subjected said dry residue to the action of dioxygen of the air in the presence of OH − ions and the suspension obtained is subjected to an acid treatment and then to dehydration so as to obtain a reagent practically devoid of manganese in the form Mn 2 O 4 or Mn 2 O 3 [<3%] comprising manganese with a degree of oxidation (IV) (Mn (IV)).

10. Composition according to claim 1 , wherein the method further comprises:

a step j) of mixing or treating the ash obtained from step c) in an acid medium with a support in order to obtain a supported catalyst, or

a step (k) of reacting the ash obtained from step c) with ligands, in order to obtain chelated agents.

11. Composition according to claim 6 , wherein the method further comprises:

a step j) of mixing or treating the dry residue obtained from step e) or step f) in an acid medium with a support in order to obtain a supported catalyst, or

a step (k) of reacting the dry residue obtained from step e) or step f with ligands in order to obtain chelated agents.

12. Composition according to claim 9 , wherein the method further comprises:

a step j) of mixing or treating the dry residue obtained from step g) or step h) in an acid medium with a support in order to obtain a supported catalyst, or

a step (k) of reacting the dry residue obtained from step g) or step h) with ligands, in order to obtain chelated agents.

13. Composition according to claim 1 , wherein the step c) of heat treatment is carried out in an oven at a temperature below 500° C.

14. Composition according to claim 1 , wherein the plant is selected from the group consisting of Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea meissnerimeisneri, Maytenus fournieri drakeana, Maytenus fournieri fournieri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis ), Bridelia ferruginea, Lantana camara, Psorospermun febrifugum Spach, Macadamia neurophylla, Phytolacca americana, Gossia bidwilii; Phytolacca acinosa Roxb, Virotia neurophylla, Macadamia integrifolia, macadamia tetraphylla, Eleutherococcus sciadophylloides (synonym Acanthonanax sciadophylloides ), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, Maytenus cunninghamii, Chengiopanax sciadophylloides, Phytolacca americana, Austromyrtus bidwiliii, Alyxia rubricauLia, Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, Dipteris conjugata, Eugenia Clusioides, Pinus sylvestris, Stenocarpus ndnei, Virotia neurophylla, Schima superba , and Polygonuum hydropiper.

15. Composition according to claim 1 , wherein the plant is Grevillea exul ssp. exul and the concentration of Mn in dried leaves of the plant Grevillea exul ssp. exulis between 15,000 and 280,000 mg/kg of plant dry weight.

16. Composition according to claim 1 , wherein said composition is a catalyst.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 27, 2023
From: GRISON, CLAUDE; ESCANDE, VINCENT
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITE MONTPELLIER 2 SCIENCES ET TECHNIQUES
Reel/Frame 064076/0897 →
CHANGE OF NAME Recorded Jun 27, 2023
From: UNIVERSITE MONTPELLIER 2 SCIENCES ET TECHNIQUES
To: UNIVERSITÉ DE MONTPELLIER
Reel/Frame 064077/0145 →
Priority Claims (1)
FR 12/57135 · Jul 23, 2012 · national
Continuity (2)
Division 14416404
Related Publication 20200290032A1 · Sep 17, 2020