Uses of certain platinoid accumulating plants for use in organic chemical reactions

Patent metadata

Field	Value
Publication number	US-2016159934-A1
Application number	US-201414905119-A
Country	US
Kind code	A1
Filing date	Jul 15, 2014
Priority date	Jul 15, 2013
Publication date	Jun 9, 2016
Grant date	—

Abstract

A composition derived from the acid treatment of ashes obtained after heat treatment of selected plants or plant material is provided. The selected plants accumulate metal from the platinum group (platinoids). The compositions can be used to produce catalysts for performing various organic synthesis reactions.

First claim

1 . A method of performing organic synthesis reactions utilizing a composition as a catalyst, the composition comprising a metal catalyst originating after acid treatment of ashes obtained after heat treatment of a plant or part of a plant belonging to one of the genera chosen from green arrow arum ( Peltandra virginica ), cucumber ( Cucumis sativus ), garden cress ( Lepidium sativum ), Canadian pondweed ( Elodea canadensis ), spinach ( Spinacia oleracea ), water hyacinth ( Eicchornia crassipes ), alfalfa ( Medicago sativa ), maize ( Zea mays ), white mustard ( Sinapis alba ), brown mustard ( Brassica juncea ), barley ( Hordeum vulgare ), nettle ( Urtica dioica ), lacy phacelia ( Phacelia tanacetifolia ), radish ( Raphanus sativus ), perennial rye-grass ( Lolium perenne ), Italian rye-grass ( Lolium multiflorum ), hooked bristlegrass ( Setaria verticillata ) and tobacco ( Nicotiana tabacum ), preferably white mustard ( Sinapis alba ), brown mustard ( Brassica juncea ), Italian rye-grass ( Lolium multiflorum ),
said plant having accumulated at least one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium, rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh), the metal catalyst comprising metal or metals of which are chosen from the metals originating from said plant, and the metal or metals of which present in the composition originate exclusively from the plant before calcination and preferably without the addition of metal coming from an origin other than said plant.

2 . The method according to claim 1 characterized in that the heat treatment of a plant or part of a plant is carried out in air.

3 . The method according to claim 1 characterized in that the heat treatment of a plant or part of a plant is carried out under an inert gas atmosphere, preferably argon.

4 . A method of performing organic synthesis reactions utilizing a composition prepared by heat treatment in air of a plant or part of a plant belonging to one of the genera chosen from green arrow arum ( Peltandra virginica ), cucumber ( Cucumis sativus ), garden cress ( Lepidium sativum ), Canadian pondweed ( Elodea canadensis ), spinach ( Spinacia oleracea ), water hyacinth ( Eicchornia crassipes ), alfalfa ( Medicago sativa ), maize ( Zea mays ), white mustard ( Sinapis alba ), brown mustard ( Brassica juncea ), barley ( Hordeum vulgare ), nettle ( Urtica dioica ), lacy phacelia ( Phacelia tanacetifolia ), radish ( Raphanus sativus ), perennial rye-grass ( Lolium perenne ), Italian rye-grass ( Lolium multiflorum ), hooked bristlegrass ( Setaria verticillata ) and tobacco ( Nicotiana tabacum )
said plant having accumulated at least one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium, rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh) and containing at least one mono- or polymetallic agent, the metal or metals of which are chosen from the metals originating from said plant and the metal or metals of which present in the composition originate exclusively from the plant before heat treatment and without the addition of metal coming from an origin other than said plant.

5 . The method according to claim 1 characterized in that the acid treatment is preferably carried out with hydrochloric acid, in particular gaseous HCl, 1N to 12N HCl, sulphuric acid, trifluoromethanesulphonic acid, nitric acid, perchloric acid, phosphoric acid, trifluoroacetic acid, para-toluene sulphonic acid, acetic acid, formic acid, oxalic acid or a mixture of acids such as the hydrochloric acid-nitric acid mixture or the acetic acid-nitric acid mixture preferably used at a high concentration preferably from 10 to 30%.

6 . Method for the preparation of a composition comprising a metallic or polymetallic agent comprising at least one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium, rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh) characterized in that it comprises the following steps:
a) Dehydration, preferably at ambient temperature or in an oven at a temperature of the order of 70° C., of the biomass comprising the leaves, stems and/or roots of a plant or an extract from a plant, the plant belonging to one of the genera chosen from green arrow arum ( Peltandra virginica ), cucumber ( Cucumis sativus ), garden cress ( Lepidium sativum ), Canadian pondweed ( Elodea canadensis ), spinach ( Spinacia oleracea ), water hyacinth ( Eicchornia crassipes ), alfalfa ( Medicago sativa ), maize ( Zea mays ), white mustard ( Sinapis alba ), brown mustard ( Brassica juncea ), barley ( Hordeum vulgare ), nettle ( Urtica dioica ), lacy phacelia ( Phacelia tanacetifolia ), radish ( Raphanus sativus ), perennial rye-grass ( Lolium perenne ), Italian rye-grass ( Lolium multiflorum ), hooked bristlegrass ( Setaria verticillata ) and tobacco ( Nicotiana tabacum ) having accumulated one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium, rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh); and, optionally, b) Grinding of the dry biomass of a plant or of an extract from a plant obtained in step a) optionally in the presence of a salt or of a mixture of salts, preferably sodium chloride and potassium disulphate, c) Heat treatment in air or under an argon atmosphere of the biomass obtained in step a) or of the ground mixture obtained in step b) in an oven preferably in one or more steps preferably in one step at 500-600° for several hours, preferably for approximately 2 hours or in two steps, the first at a temperature of less than 500° C. preferably of the order of 350° and the second step at a temperature of the order of 550° each of these steps being carried out for approximately 3 hours; and, optionally, d) Treatment of the ashes obtained in step c) with a salt or a mixture of several salts preferably a mixture of sodium chloride and potassium disulphate so as to obtain a molten mixture after heating; and, optionally, e) Treatment of the ashes obtained in step c) or of the molten mixture obtained in step d) with an acid solution, said acid being preferably chosen from hydrochloric acid preferably at a concentration chosen between 1 M and 12 M or nitric acid, sulphuric acid, trifluoromethanesulphonic acid, nitric acid, perchloric acid, phosphoric acid, trifluoroacetic acid or para-toluene sulphonic acid, acetic acid, formic acid, oxalic acid or a mixture of acids such as the hydrochloric acid-nitric acid mixture or the acetic acid-nitric acid mixture, these acids preferably being used at a high concentration preferably from 10 to 30%, treatment followed if desired, by filtration preferably on celite and dehydration of the solution or suspension obtained preferably under reduced pressure so as to obtain a dry residue which can be dried at 120° C.; and, optionally, f) Action on the product obtained in step c), d) or e) of acetic acid in the presence of a strong acid, preferably nitric acid, in order to obtain, after concentration under reduced pressure, a solid which is then taken up in an organic solvent, preferably acetone or ethyl acetate in order to produce, after evaporation, a product in the form of acetate; and, optionally, g) Reaction of the product obtained in step e) containing rhodium with triphenylphosphine in order to obtain a pure complex of formula RhCl(PPh 3 ) 3 by precipitation; and, optionally, h) Mixing or treating the product obtained in step c), d), e), f) or g) in an acid medium with a mineral support chosen from montmorillonite K10, silica, alumina or hydrotalcite or an organic support preferably chitosan or preferably, a carbon support in order to obtain, after filtration, then drying in an oven or under vacuum a catalyst supported on a mineral or organic support; and, optionally, i) Total or p

Assignees

• Centre Nat Rech Scient
• Univ Montpellier Ii

Inventors

• Grison Claude
• Escande Vincent
• Bes Clemence
• Renard Brice-Loic

Classifications

• C22B3/18

  with the aid of microorganisms or enzymes, e.g. bacteria or algae · CPC title

• C22B11/04

  by wet processes (extraction of metal compounds by leaching in organic solutions C22B3/16; treatment or purification of solutions by liquid-liquid extraction C22B3/26) · CPC title

• B01J37/30

  Ion-exchange · CPC title

• C02F2101/10

  Inorganic compounds · CPC title

• B01J37/36 Primary

  Biochemical methods · CPC title