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    • 专利摘要:
    The invention relates to the use of a material of plant origin rich in phenolic acids for the implementation of organic chemistry reactions as well as for the recycling of catalysts. The invention also relates to the use of an effluent of extractive or industrial origin as a reaction medium for carrying out a chemical reaction,
    公开号:FR3064497A1
    申请号:FR1800053
    申请日:2018-01-15
    公开日:2018-10-05
    发明作者:Claude Grison；David Carrasco；Andrii STANOVYCH
    申请人:Centre National de la Recherche Scientifique CNRS；
    IPC主号:
    专利说明:

    Holder (s): NATIONAL CENTER FOR SCIENTIFIC RESEARCH.
    Extension request (s)
    Agent (s): CABINET LAVOIX Simplified joint-stock company.
    USE OF MATERIALS OF PLANT ORIGIN RICH IN PHENOLIC ACIDS FOR THE IMPLEMENTATION OF ORGANIC CHEMICAL REACTIONS AND THE RECYCLING OF CATALYSTS.
    The invention relates to the use of a material of plant origin rich in phenolic acids for the implementation of organic chemistry reactions as well as for the recycling of catalysts. The invention also relates to the use of an effluent of extractive or industrial origin as a reaction medium for carrying out a chemical reaction,
    FR 3 064 497 - A1
    USE OF PLANT-GENETIC MATERIALS RICH IN PHENOLIC ACIDS FOR THE IMPLEMENTATION OF ORGANIC CHEMISTRY REACTIONS AND THE RECYCLING OF CATALYSTS
    The invention relates to the use of a material of plant origin rich in phenolic acids for the implementation of organic chemical reactions as well as for the recycling of catalysts.
    The biological decontamination of industrial and mining waste and discharges as well as the treatment of effluents contaminated with metallic residues are very worrying problems.
    Among the various polluting substances, transition metals are among the most harmful compounds, because they are not biodegradable.
    Different phytoremediation techniques (phytoextraction, phytodegradation, phytostabilisation, phytostimulation, phytotransformation, phytovolatilisation and rhizofiltration) are currently in full development (Terry, N. and Banuelos G., editors, Phytoremédiation of contaminated soil in water, Lewis Publishers, Boca Raton, F1 .2000).
    The CNRS team, author of the present invention, studied in particular the plant Thlaspi caerulescens (synonym Noccaea caerulescens) belonging to the Brassicaceae family which has remarkable properties of tolerance and hyperaccumulation of zinc, cadmium, nickel. It concentrates them on the aerial parts (leaves and stems).
    This plant is capable of storing zinc at concentrations 100 times higher than that of a conventional plant. In addition, it is able to extract and concentrate zinc and cadmium in aerial tissues, even on soils with a low concentration of these two metals.
    In addition, heavy metals are commonly used in organic chemistry as essential catalysts for carrying out chemical transformations which require significant activation energy. The role of the catalysts is then to lower the energy barrier.
    In international applications WO 2011/064462 and WO 2011/064487 published on June 3, 2011 is described and claimed the invention of Professor Grison and Doctor Escarré relating to the use for the first time of a calcined plant or a part of it. calcined plant having accumulated at least one metal in the form M (II) chosen in particular from zinc (Zn), nickel (Ni) or copper (Cu), lead (Pb), for the preparation of a composition containing at minus a metal catalyst, the metal of which is one of the above metals in M (II) form originating from said plant, said composition being devoid of chlorophyll, and allowing the implementation of organic synthesis reactions involving said catalyst.
    Application WO 2011/064487 describes the use of numerous other metallophyte plants hyperaccumulating heavy metals for the preparation of catalysts usable in organic chemistry.
    As a result, plant waste is directly recovered and transformed into “green” catalysts or unconventional reagents.
    In international application WO 2013/150197, the team of Professor Grison has shown that, unexpectedly, certain other plants which belong to the genus Sedum as well as a different plant, Potentilla griffithii, have metallophyte properties hyperaccumulative of heavy metals which make them particularly interesting for use in catalysis in organic chemistry.
    In international application WO 2014/128283, Professor Grison's team then discovered that certain plants chosen from Psychotria douarrei, Geissois Pruinosa, Alyssum mural, Noccaea caerulescens and Anthyllis vulneraria had the property of accumulating large amounts of Nickel (Ni) and could be used for the preparation of catalysts usable in organic chemistry.
    In addition, the chemistry of platinoids brings together an essential field of organic synthesis, that of reactions catalyzed by precious metals: platinum, palladium, osmium, iridium, ruthenium and rhodium. This field of chemistry is essential to all sectors of fine chemistry: pharmacy, food, agrochemistry, cosmetics and perfumery.
    However, access to resources has become a key problem: they are mainly concentrated in a limited number of countries, often politically unstable. World resources are in the process of depletion; ore mining is driven by rising energy costs. This general context is leading to a record increase in the cost of production.
    Faced with such a situation, the development of innovative recycling processes for platinoids is of considerable importance.
    In application WO 2015/007990, the inventors have demonstrated the effectiveness of plants which accumulate platinoid metals, in particular in their roots, for the treatment of degraded mining sites or polluted aqueous environments. The compositions prepared and containing at least one metal catalyst, obtained after heat treatment of said plants, can be used in organic synthesis reactions.
    Said hyperaccumulative plants of platinoids belong to one of the genera chosen from green arum (Peltandra virginicà), cucumber (Cucumis sativus), watercress (Lepidium sativum), elodée du Canada (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchomia crassipes), alfalfa (Medicago sativà), corn (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Raphanus sativus), common ryegrass (Lolium perenne), Italian ryegrass (Lolium multiflorum), whorled foxtail (Setaria verticillata) and tobacco (Nicotiana tabacum).
    These varieties of plants are either cultivated in the presence of contaminated effluents or in a sterile medium watered by the effluents contaminated by one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium, rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh), so as to accumulate said metals in the leaves, stems and / or roots.
    The inventors of the present application have found a new way of valuing plants which fix metal cations without cultivating said plants on degraded mining sites, or in polluted aqueous media. It is now possible to simply put in contact a medium containing metal cations, for example an effluent contaminated by platinoids with materials of plant origin which are no longer the whole living plants, but for example the roots of metal-fixing plants. , crushed and dried in the form of a powder.
    Indeed, the inventors of the present application have discovered that the biosorption of these transition metals most probably had its origin in the presence of natural or functionalized phenolic acids in these plants capable of fixing metals in ionic form.
    The term "biosorption" used in the present invention represents the non-physiological physicochemical process, by which plants and or plant materials rich in phenolic acids of the present invention adsorb certain metals.
    After various studies, they have thus shown that this biosorption is dependent on the chemical composition of plant materials used for the extraction of metals present in environments rich in metals. Among the plant materials rich in phenolic acids, mention may be made of the roots of aquatic plants, in particular water hyacinth (Eicchomia crassipes) or water lettuce (Pistia stratiotes); materials rich in tannins such as coffee grounds, green and black tea leaves, grape musts; materials rich in lignin such as cereal straw such as wheat straw, coconut or hemp fluff; fiber plants; the woods of deciduous trees such as birch, chestnut, eucalyptus; wood-derived wastes including sawdust from poplar, agave, pine or sorghum, cones of conifers such as pine cones, bugs such as those of chestnut trees.
    For the purposes of the present invention, the term “phenolic acids contained in plant materials” means structures of plant origin, insoluble in water, comprising an aromatic carbon skeleton (rich in phenolic derivatives) and having at least acid groups. naturally occurring carboxylic or derived from a chemical modification to enrich the carbon skeleton in carboxylic acid functions.
    "Plant materials" can be divided into three main families:
    the polymeric structures constituting the roots of certain aquatic plants (examples: roots of water hyacinths or water lettuces): materials 1
    - tannins (examples: coffee and tea grounds): materials 2 natural materials rich in lignin (wheat straw, pine cones, coconut fluff ...): materials 3
    The definition of phenolic acids can be made on the basis of infrared spectral data. The presence of phenolic acids in the plant materials of the present invention can be determined based on their infrared (IR) spectral data. The principle is based on the comparison of the intensities of the vibration bands of the aromatic cycle (3 characteristic bands between 1600 and 1400 cm ' 1 ) and that of the C = O bond of the carboxylic acid unit (located between 1680 and 1620 cm' 1 , according to the degree of conjugation) for a given material of plant origin.
    As an illustration, the following table summarizes these data:
    Materials 1 IR data of the C = O band of the COOH group (cm 1 ) IR data of the aromatic cycle (cm ' 1 ) Comments Water hyacinth roots 1620(Absorbance A = 8.6%) 1512(A = 3.0%)1414(A = 5.1%) The intense and wide band at 1620 cm ' 1 covers the aromatic band at 1600 cm' 1
    Roots ofwater lettuces 1626(A = 11.5%) 1513(A = 8.8%)1416(A = 10.7%) Id.
    The intensity of the band at 1620 is much higher than that of the bands at 1512 and 1414: this type 1 biomaterial is considered to be "rich in phenolic acids".
    Materials 2 IR data of the C = O band of the COOH group (cm 1 ) IR data of the aromatic cycle (cm 1 ) Comments coffee grounds 1645(A = 8.2%) 1525(A = 5.6%)1443-1414 (A = 7.3%) Tea marc 1626(A = 7.2%) 1517(A = 5.5%)1455(A = 6.4%) Id.
    The intensity of the strip at 1645 is much higher than that of the strips at 1525 cm -1 and 1443-1414 cm 1 : this type 2 biomaterial is considered to be “rich in phenolic acids”.
    Materials 3 IR data of the C = O band of the COOH group (cm 1 ) IR data of the aromatic cycle (cm 1 ) Comments Conclusions Wheat straw 1654(A = 2.9%) 1598(A = 2.8%)1510(A = 2.8%)1426(A = 3.5%) The intensity of the strip at 1654 cm -1 is less than that of the strip at 1426 cm -1 : this raw biomaterial is not considered to be “rich in phenolic acids” and is only useful after functionalization. Cones 1658 1602 The intensity of the strip at 1658 cm ' 1
    (A = 4.6%) (A = 5.6%)1510(A = 5.6%)1441-1419(A = 6.2%) is lower than that of the bands at 1602, 1510 and 1441-1419 cm ' 1 : this raw biomaterial is not considered to be “rich in phenolic acids” and is only useful after functionalization
    The expression “rich in phenolic acids” within the meaning of the present invention designates contents of phenolic acid present in materials of plant origin, for example, a powder of plant roots, in particular water hyacinth, determined by considering the intensity ratios between the bands at 1654 cm ' 1 / 1601-1510-1426 cm' 1 and 1645 cm ' 1 / 1525-14431414 cm' 1 for wheat straw and coffee grounds. The IR analysis makes it possible to retain coffee grounds as a material of plant origin "rich" in phenolic acid. Wheat straw must be functionalized with a polyacid to be classified as a material of plant origin "rich" in phenolic acid.
    Thus within the meaning of the present application, a material of plant origin rich in phenolic acids is a material of plant origin for which the intensity of said bands characteristic of the valence vibration of the (C = O) of carboxylic acids is greater than the intensity of said bands characteristic of the valence vibration of the aromatic cycle, for example for plant materials of types 1 and 3. The reference material (of type 3) is not considered to be rich in phenolic acids within the meaning of present invention because the intensity of the strip at 1658 cm 1 is lower than that of the strips at 1602, 1510 and 1441-1419 cm ' 1 . Figure 1 easily illustrates the selection criterion based on the intensity ratios (absorbance) between the bands at 1654 / 1601-1510-1426 cm ' 1 and 1645 / 1525-1443-1414 cm' 1 for wheat straw and coffee grounds. IR analysis makes it possible to retain coffee grounds as a material of plant origin rich in phenolic acids. Wheat straw must be functionalized with a polyacid to be classified as a material of plant origin rich in phenolic acids.
    A person skilled in the art is able to determine whether the material of plant origin is sufficiently rich in phenolic acids to have the functional capacity to fix at least
    90%, 95% or preferably 100% of the metal (s) present in the aqueous medium to be treated. If the skilled person determines, by any known technical means available to him, that the
    Ί material of plant origin is not sufficiently rich in phenolic acids to have the functional capacity to fix at least 90%, 95% or preferably 100% of the metal or metals present in the aqueous medium to be treated, that -this can functionalize said phenolic acids, in particular using a polyacid or an acid anhydride. It is also understood that the capacity for adsorption or fixing of metals in ionic forms of the material of plant origin and therefore of the percentage of decontamination depends both on the mass of said material brought into contact with the medium containing the metals under ionic forms and the quantity by mass of metals in ionic forms contained in the medium to be decontaminated. For example, when hyacinth powder is functionalized by self-catalyzed esterification with citric acid in a nonaqueous medium, is brought into contact at a concentration of lg / L, with a liquid medium containing 94 mg / L of Ni 2+ '. it is possible to fix 55 mg of this metal in ionic form in 2 hours.
    According to the present invention, a powder insoluble in water of a material of plant origin for example, a powder of plant roots, in particular water hyacinth is obtained by grinding the roots, preferably using of a mixer mill for a few minutes in order to obtain a powder with a uniform particle size preferably between 0.5 and 1.5 mm. Then, the powder obtained is washed with water, preferably between 25 and 50 ° C, then the roots are filtered, preferably on cellulose, and the drying of said powder at a temperature between 40 and 90 ° C, by example in an oven at 80 ° C for 12 hours.
    Plants rich in tannin, are washed, filtered and dried under the same conditions as for roots.
    Plants rich in lignin, for example pine cones, are washed preferably with isopropanol in order to remove resin acids. They are then ground using a blender mill for a few minutes. The powder is again washed preferably with isopropanol, then with hot water, filtered through cellulose, before being dried in an oven at 80 ° C. for 12 hours.
    The materials of plant origin of the present invention, for example, a powder of plant roots, in particular water hyacinth, makes it possible to clean up in a few hours media highly contaminated with at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium ( Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury ( Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb ), cerium (Ce).
    The expression "a metal in ionic form" means a metal in the form M (I), M (II), Μ (ΠΙ), M (IV), M (V) or M (VI).
    The inventors of the present application have therefore shown that the use of materials of plant origin ground and packaged in the form of powder, for example, a powder of roots of aquatic plants, in particular water hyacinth, makes it possible to fix the metals chosen in particular among scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) more effectively in comparison with the use of living plants which fix metals by rhizofiltration.
    The development of metal cation fixing plants according to the present invention offers at least one advantage compared to previous implementations of metal cation fixing plants to obtain biocatalysts:
    the bio-sourced catalysts of the present invention make it possible to carry out organic synthesis reactions in the presence of catalysts in a recyclable homogeneous phase, whereas generally, the homogeneous catalysis does not make it possible to separate the catalyst from the reaction medium, because the catalyst is in the same phase as the reactants and the products of the catalyzed reaction. However, in the present case, the metal catalyst is easily recoverable by bringing a material of plant origin into contact in the form of a powder of plant waste, for example coming from the roots of certain aquatic plants (examples: roots water hyacinths or water lettuce), vegetable waste rich in tannins (examples: coffee and tea grounds) or vegetable waste rich in lignin (wheat straw, pine cones, coconut fluff) with the reaction medium after catalysis to recover the metal / material complex of plant origin rich in phenolic acids isolubied by simple filtration and rinsing, thus the biosourced catalysts in homogeneous phase of the present invention are recyclable.
    Furthermore, the performance of these bio-based catalysts is often superior to that of their commercial counterparts of non-vegetable origin. In fact, the catalysts of the present invention have better catalytic activity, for example the biobased catalyst according to the invention is active, for example from 0.001 mol%, preferably from 0.0025 to 0.01 mol% of palladium in the M form. (II).
    The biomaterials used in the present invention are materials of plant origin in the form of a powder obtained after grinding and drying of the plant raw material, the phenolic acid content within the meaning of the present invention, being determined by a person skilled in the art. medium infrared spectrum, for example.
    The present subject therefore has the first object, a process for the preparation of a material of plant origin having fixed at least one metal in ionic form, characterized in that it comprises the following steps:
    - Add a material of plant origin in the form of a powder insoluble in water, in an amount sufficient to fix said at least one metal in ionic form, in an aqueous liquid medium containing at least one metal chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru ), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg ), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb) , cerium (Ce),
    - Leave the said insoluble powder to act in said aqueous liquid medium containing at least one of said metal for at least one hour, preferably between 1 and 2 hours or at least 2 hours, at a positive temperature, preferably between 10 and 30 ° C. , preferably at 20-25 ° C.
    - Filtering said aqueous medium to recover said powder having fixed at least 90%, preferably 100% of said metal present in said aqueous liquid medium, in "batch" mode, on a column.
    Materials of plant origin, for example, a powder of roots of aquatic plants, in particular water hyacinth or materials rich in tannins and / or lignins, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru ), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg ), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb) , cerium (Ce), are directly valued by ecocatalysis. Plant materials, especially root powders, are preferably heat treated (reduced to ashes), after possible dehydration, activated and used in chemical catalysis for the synthesis of biomolecules with high added value. The opportunities derived from the new type of biomass proposed are numerous and give rise to a considerable number of possibilities in acid catalysis, green oxidations, redox reactions, and couplings, and in particular in the homogeneous phase.
    According to the present application, the process for the preparation of a material of plant origin having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt ( Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir ), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium ( Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce), is characterized in that it further comprises a treatment thermal to obtain ash and optionally an acid treatment.
    Within the meaning of the present invention, the heat treatment is carried out in air or under an argon atmosphere of a material of plant origin (root powders for example) in an oven preferably in one or more stages preferably in one step at 500-800 ° C for 2 to 8 hours, preferably for 4 to 6 hours or in two steps the first at a temperature below 500 ° C, preferably around 350 ° C and at a second stage at a temperature of the order of 550 ° C. each of these stages being carried out for approximately 3 hours. Preferably, the heat treatment corresponds to a calcination of the biomass at 550 ° C. for 6 h.
    A catalyst according to the present invention corresponds to the product obtained by the process for the preparation of a material of plant origin having fixed at least one metal in ionic form, chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd ), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce).
    Another subject of the present application is the use as a catalyst and in particular in the homogeneous phase, of a composition containing a metallic catalyst originating, optionally after acid treatment, from the ash obtained by heat treatment of a material of vegetable origin, under the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated, rich in phenolic acids, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal of the lanthanide series n in particular europium (Eu), ytterbium (Yb), cerium (Ce), a metallic catalyst whose metal or metals are chosen from the metals originating from said material and whose metal or metals present in the composition of l he invention comes exclusively from material of plant origin and without adding metal from another origin than said material for the implementation of organic synthesis reactions involving said catalyst.
    The present application also relates to a process for carrying out organic synthesis reactions comprising the preparation of a composition containing a metallic catalyst originating, optionally after acid treatment, from the ash obtained by heat treatment of said material of plant origin, in the form of a powder insoluble in water, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (L ·), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) metal catalyst whose metal or metals are chosen from among i the metals originating from said material and of which the metal or metals present in the composition of the invention come exclusively from material of plant origin and without adding metal originating from another origin than said material for carrying out reactions organic synthesis involving said catalyst, especially in homogeneous phase.
    A subject of the invention is also the use as described above or the method as described above characterized in that the material of plant origin in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids is preferably chosen from the powder of plant roots, in particular water hyacinth (Eicchornia crassipes) or water lettuce (Pistia stratiotesf coffee grounds, green and black tea leaves, grape must; lignin including functionalized lignin which is insoluble in water; and materials rich in lignin such as cereal straw such as wheat or hemp straw; fiber plants; the hardwoods of deciduous trees such as birch, chestnut, eucalyptus; sawdust including poplar sawdust, d 'agav e, pine or sorghum; cones such as pine cones, preferably after functionalization of the phenolic acids present in said material of plant origin.
    The subject of the invention is also reuse as described above or the process as described above, characterized in that said material of plant origin rich in phenolic acids is preferably powder of hyacinth roots from water or water lettuce, preferably water hyacinth and in that, preferably:
    the powder preferably from the ends of the roots is used the roots are devoid of aerial parts and / or the material has undergone dehydration before use.
    It has been observed that the biomaterials used can be functionalized in order to increase the affinity of metal cations for the biosorbent.
    A subject of the invention is also the use as described above or the process as described above characterized in that the phenolic acids contained in said material of plant origin have been functionalized before fixing at least one metal and in that the functionalization of said phenolic acids is preferably carried out by a reaction of the type
    Mannich such as the Betti reaction, by a diazo coupling reaction, by a cross-functionalization reaction such as the transition from an ester to an amide, the use of amino residues such as dipicolylamine to introduce nitrogenous ligends , by using amino residues for the introduction of a sulfonic group by addition to propane sulfone, by the direct use of taurine, by oxidation of said amino residues such as the oxidation of the pyridine nucleus to pyridine oxide, by phosphorylation, by esterification, by alkaline hydrolysis, by isothiocyanation, by halogenation, by nitration by carboxylation using mixed, cyclic, aliphatic, functionalized anhydrides, generated in situ or previously.
    The subject of the invention is also reuse as described above or the method as described above characterized in that the phenolic acids contained in said material of plant origin have been functionalized before fixing at least a metal in ionic form and in that the functionalization of said phenolic acids is preferably carried out by the introduction of a functional group chosen from:
    aliphatic, cyclic, heterocyclic or aromatic amino, aminoalcohol or di-polyamino groups introduced by a Mannich or related reaction such as the Betti reaction or by a transfunctionalization reaction the oxime groups the hydroxamic groups the sulfonic groups by a Mannich reaction or related preferably using taurine or by diazo coupling or by sodium sulfite reaction the heterocyclic groups introduced by a Mannich reaction or by nucleophilic substitution or by addition-elimination of the amide, urea or thiourea, thiocyanate, nitro or halogen groups the carboxylic functions introduced using an acid anhydride or a diacid or derivative of diacid or triacid, derivative of triacid which can be polyfunctional, including nitrogen, sulfur or phosphorus, prepared in situ or previously in non-aqueous medium
    - phosphorus radicals introduced by reaction of a phosphorylation reagent having a phosphoric anhydride group such as P2O5 or polyphosphoric acid functionalized or not or by grafting of P (III) derivatives, by esterification of hydroxy groups or by a donor phosphate such as acetylphosphate, creatine
    Thiols introduced by a Mannich or related reaction such as the reaction of
    Betti.
    A subject of the invention is also the use as described above or the method as described above characterized in that the medium in which said material of plant origin in the form of an insoluble powder in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium ( Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury ( Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb ), the cerium (Ce) is either a reacted medium onnel in which a chemical reaction using a metal catalyst has been carried out either an effluent from a reaction medium in which a chemical reaction using a metal catalyst has been carried out, or an effluent of extractive or industrial origin comprising metallic elements.
    A subject of the invention is also the use as described above or the method as described above characterized in that the medium in which said material of plant origin in the form of an insoluble powder in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated has fixed at least one metal is either a reaction medium in which a chemical reaction using a metal catalyst has been carried out either an effluent from a reaction medium in which a chemical reaction using a metal catalyst has been carried out and in that the metal in fixed ionic form is chosen in particular from scandium (Sc), manganese (Mn ), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum e (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce).
    The invention also relates to the use as described above or the method as described above characterized in that the medium in which the material of plant origin in the form of an insoluble powder in water in sufficient quantity to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids has fixed at least one metal is an effluent of extractive origin or industrial comprising metallic elements and in particular an effluent from a quarry and in that the fixed metal is chosen in particular from iron (Fe), manganese (Mn), zinc (Zn), nickel (Ni), copper (Cu), lead (Pb), scandium (Sc), cerium (Ce) and lithium (Li), or osmium (Os).
    A subject of the invention is also the use as described above or the process as described above characterized in that the organic synthesis reactions involving said catalyst are chosen from redox reactions such as oxidation, in particular the oxidation of alcohols, oxidative cleavages, epoxidation, reduction reactions, Lewis acid catalysis reactions, cross-coupling and homocoupling reactions such as reactions for forming carbon-carbon bonds such as than the Suzuki reaction, the Heck reaction, the Sonogashira reaction, the formation of nitrogen-carbon, oxygen-carbon bonds, polymer constructions such as polycondensations, reactions involving Lewis acid catalysis preferably chosen from aromatic electrophilic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions s, cascade reactions, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as the condensation reactions of an aldehyde on a di-activated compound of Knoevenagel type, the Perkin reaction , the Tollens reaction, the Thorpe reaction, the Claisen reaction, or the Mukaiyama reaction.
    multistage reactions including an oxidation or reduction reaction followed by Lewis acid catalysis isomerization reactions insertion reactions.
    A subject of the invention is also the use as described above or the process as described above comprising the preparation as catalyst, of a composition containing a metal catalyst originating, optionally after acid treatment, from the ash obtained by heat treatment of a material of plant origin in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper ( Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt ), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), l aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce), characterized in that the organic synthesis reactions involving said catalyst are chosen from :
    oxidation reactions reduction reactions cross-coupling and homocoupling reactions such as carbon-carbon bond formation reactions such as the Suzuki reaction, the Heck reaction, the Sonogashira reaction, polymerizations, polycondensations reactions involving Lewis acid catalysis preferably chosen from electrophilic aromatic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, transfunctionalization reactions, esterifications , carboxylations, halogenations, nitrations, thiocyanations, aldolization or crotonization reactions or related reactions, preferably Knoevenagel reactions, Perkin reactions, Claisen reactions, Tollens reactions or Thorpe reactions- Ziegler.
    multistage reactions including an oxidation or reduction reaction followed by Lewis acid catalysis isomerization reactions
    A subject of the invention is also the use as described above or the method as described above characterized in that the material of plant origin in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids having fixed a metal in fixed ionic form chosen in particular from scandium (Se), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium ( Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce ), is used in org synthesis reactions anique of functional transformations by catalysis chosen from oxidation reactions such as Wacker-Tsuji oxidation, alcohol oxidation, oxidative coupling of aromatic compounds, reduction such as reduction of olefins and nitro compounds and nitriles or hydrosilylation of olefins and alkynes, catalytic hydrogenation, cross-coupling and homocouplings such as carbon-carbon bonding reactions such as Suzuki reaction, Heck reaction, reaction from Sonogashira the nucleophilic addition reactions of an enamine on piallylic complexes, Buchwald-Hartwig type reactions, carbonylation and ene-reaction reactions, regioselective reactions between an alkene and an aromatic derivative, cyclopropanation of alkenes , cycloadditions, cascaded carbocylization of polyunsaturated compounds, allylic isomerization, cycloaddition, en-reactions, cycloisomerizations, hydroboration, polymerization reactions, polycondensations, syntheses of unsaturated and conjugated polymers.
    A subject of the invention is also the use as described above or the method as described above characterized in that the material of plant origin in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids having fixed a metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd ), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic ( As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) is used in organic synthesis reactions of functional transformations by catalysis chosen from the following reactions: oxidation reactions, reduction reactions, cross-coupling and homocoupling reactions, reactions involving Lewis acid catalysis preferably chosen from electrophilic substitution reactions aromatic (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as condensation reactions of an aldehyde on a compound diactivated type Knoevenagel, the reaction of Perkin, the reaction of Tollens, the reaction of Thorpe, the reaction of Claisen, or the reaction of Mukaiyama; combination reactions of oxidation or reduction by Lewis acid catalysis, brominations, protections such as chemoselective tritylations of alcohols and amines, acylations, in particular acetylations of alcohols, phenols, thiols and amines, silylations of alcohols, oximes, enolates, phenols, amines and anilines, the formation of imines or amines, deprotection of functions, in particular detritylation, concerted rearrangements such as ene-reactions or cycloadditions, pinacolic or Beckmann transposition, the Claisen-Schmidt reaction the Mukaiyama reaction or Knoevenagel-type reactions, dehydration or transfunctionalization reactions such as transamination or transtritylation reactions, reactions for the preparation of polyheterocyclic structures such as porphyrinogens or dithienylpyrroles, multicomponent reactions such as the synthesis reactions of triazoles, the Hantzsch reactions, the synthesis of optionally substituted piperidines, the biomimetic reactions and of hydride transfers.
    A subject of the invention is also the use as described above or the method as described above characterized in that the material of plant origin in the form of a powder insoluble in water in sufficient quantity to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids having fixed a metal in ionic form chosen in particular from scandium (Se), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd ), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic ( As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) is used in organic synthesis reactions of functional transformations by Lewis acid catalysis chosen oxidation reactions, reduction reactions, cross coupling and homocoupling reactions, aromatic electrophilic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, reactions in cascade, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as the condensation reactions of an aldehyde on a diactivated compound of Knoevenagel type, the Perkin reaction, the Tollens reaction, Thorpe's reaction, Claisen's reaction, or Mukaiyama's reaction; oxidation or reduction combination reactions, aromatic electrophilic substitution reactions, the construction of heterocycles, the preparation and protection of carbonyl derivatives, radical oxidations, epoxidation, oxidation of alcohols located in alpha of an aromatic group heterocyclic or carbocyclic or of a double bond, the oxidative cleavages of polyols, the oxidation of benzamines, the aromatic oxidative dehydrogenation of unsaturated and / or conjugated cyclic derivatives optionally comprising a heteroatom, the direct halogenation of enolisable compounds, the reaction of Hantzsch in Lewis acid catalysis between an aldehyde, a beta-dicarbonyl compound and a source of ammonium leading to the formation of dihydropyridines (DHP).
    A subject of the invention is also the use as described above or the method as described above characterized in that the material of plant origin in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal or metals present in the liquid medium to be treated rich in phenolic acids and having fixed nickel (Ni) and optionally at least one metal in ionic form chosen among scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) is used in the s reactions chosen from reduction reactions, cross-coupling and homocoupling reactions, reactions involving Lewis acid catalysis preferably chosen from electrophilic aromatic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as condensation reactions of an aldehyde on a deactivated compound of the Knoevenagel type, the Perkin reaction, the reaction of Tollens, the reaction of Thorpe, the reaction of Claisen, or the reaction of Mukaiyama; halogenation reactions, in particular halogenation of primary, secondary and tertiary alcohols (Lucas reaction), electrophilic aromatic reactions in series, substitutions or additions, Friedel-Crafts alkylations, preferably the reaction between toluene and chloride of benzyl to obtain 4- and 2methyldiphenylmethane, Friedel-Crafts acylations preferably the synthesis of methylacetophenone, multicomponent reactions, in particular the Biginelli reaction leading to the synthesis of dihydropyrimidinones or dihydrothiopyrimidinones, preferably the
    3,4-dihydropyrimidin-2 (1H) -one or 3,4-dihydropyrimidin-2 (1H) -thione, and the Hantzsch reaction preferably used to prepare dihydropyridines, the synthesis of 5ethoxycarbonyl-6-methyl- 4-isobutyl-3,4-dihydropyrimidin-2 (1H) -one, the reaction between 3hydroxybenzaldehyde, ethyl 3-ketopentanoate and thiourea to obtain 6-methyl-4- (3hydroxyphenyl) -2-thioxo- 1,2,3,4-tetrahydro pyrimidine-5-ethyl carboxylate (monastrol), cycloaddition reactions, in particular the Diels-Alder reaction such as the reaction of cyclopentadiene with diethyl fumarate or the reaction of 3 -buten-2-one with 2,3-dimethyl1,3-butadiene, transesterification reactions, preferably the reaction of methyl palmitate and butan-1-ol, the synthesis of amino acid complexes or oximes, preferably Cu 2+ complexes of oximes, the catalyzed hydrolysis of organosulfurized functions, in particular thiophosphates such as parat hion, catalyst synthesis reactions for hydrogenation reactions after reduction of Νΐ (Π) to Ni (0), reduction reactions such as the reduction of 1-phenyl 2-nitroprene to 1-phenyl 2-aminopropane, coupling reactions comprising cross-coupling reactions, in particular the Suzuki reaction for preferably synthesizing diaryl compounds such as 3-methoxy-4'-methylbiphenyl, the Heck reaction, and the Ullmann reaction (in particular the substitutions aromatic nucleophiles such as N and O-arylations), the condensation of diamines on carbonyl derivatives, in particular the synthesis of lHl, 5-benzodiazepines preferably from Γο-phenylenediamine and acetone, the chemoselective hydrolysis of methyl esters in peptide chemistry, in particular the deprotection of carbonyl groups without cleavage of Fmoc, Fmoc-Gly-OMe and Fmoc-Gly-Phe-Pro-OMe, the chemoselective hydrolysis of the ester methyl 6,7-dideoxy-1,2,2,4-di-O-isopropyldine-7 - [(9fluorenylmethoxycarbonyl) amino] -D-glycero-aD-galacto-octopyranuronic in order to obtain an amino acid derived from galactose, synthesis of 5 'protected oligonucleotides, synthesis of 5'GpppT6 and 5'-GpppRNAs, coupling of phosphoroimidazolidate T6 on solid support with GDP in particular synthesis of 5'-guanosyl triphosphate hexa-2'-deoxythymidylate (GpppT6), Γ reducing aminations, preferably the catalyzed formation of imines followed by their reduction in situ, the synthesis of secondary amines and substituted anilines, the chlorination of alkenes such as the chlorination of dicyclopentadiene, the reactions of aromatic halogenations without dihalogen, nitration reactions without nitric and sulfuric acid, thiocyanation reactions, synthesis of bromo- and iodoanisole, successive or cascade reactions such as addition, dehydration, cycloaddition reactions, or of electrocyclization, synthesis of btenzopyranes and cannabinoids or dihydrocannabinoids and in particular the condensation of diamines on carbonyl derivatives, reductive aminations, Aromatic halogenation reactions without dihalogen, the Ullmann reaction, successive or cascade reactions such as addition reactions , dehydration, cycloaddition or cyclization, cross-coupling reactions or not such as the Suzuki reaction, aromatic electrophilic reactions in series, substitutions or additions, multicomponent reactions, in particular the Biginelli reaction.
    The subject of the invention is also a process for recycling metallic catalysts, in particular metallic catalysts comprising at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce), said process being characterized by the following stages:
    a treatment of a reaction medium in which a chemical reaction using said soluble metal catalyst has been carried out, with a material of plant origin rich in phenolic acids in the form of a powder insoluble in water in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal (s) in ionic form present in the reaction medium to be treated, and
    filtration to recover said material of plant origin rich in phenolic acids which have fixed the metal or metals in ionic form present in the reaction medium,
    - a heat treatment of said material of plant origin rich in phenolic acids, having fixed the metal or metals in ionic form to obtain ash constituting the recycled metal catalyst comprising at least one metal in ionic form chosen in particular from scandium (Sc) , manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), l arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (This).
    The invention also relates to a process for recycling metal catalysts, in particular metal catalysts comprising at least one metal chosen in particular from platinum (Pt), palladium (Pd), rhodium (Rh) and more particularly palladium (Pd) said process being characterized in that a reaction medium is treated in which a chemical reaction using said metal catalyst has been carried out or an effluent from a reaction medium in which a chemical reaction using said metal catalyst has been carried out , with a material of plant origin in the form of a powder insoluble in water rich in phenolic acids, and optionally subjected to an acid or basic treatment, the ashes obtained by heat treatment of said material of plant origin rich in acids phenolic, having fixed the metal constituting the metal catalyst comprising at least one chosen metal if in particular among platinum (Pt), palladium (Pd), rhodium (Rh) and more particularly palladium (Pd) and thus obtains the recycled catalyst
    The subject of the invention is also a process for cleaning up industrial effluents from, for example, mines, quarries or the steel industry, said process being characterized by the following stages:
    a treatment of an industrial effluent with a material of plant origin rich in phenolic acids in the form of a powder insoluble in water, preferably in an amount sufficient to fix at least 90%, 95% or preferably 100% of the metal (s) in ionic form present) in the industrial effluent to be treated, and
    -filtration to recover said material of plant origin rich in phenolic acids which have fixed the metal or metals in ionic form present in the industrial effluent.
    In order to clean up industrial effluents from, for example, mines, quarries or the steel industry and according to a preferred object of the present invention, a sufficient quantity of material of plant origin chosen from the group consisting of:
    the polymeric structures constituting the roots of certain aquatic plants (examples: roots of water hyacinths or water lettuces);
    tannins (examples: coffee and tea grounds);
    natural materials rich in lignin (wheat straw, pine cones, coconut fill).
    According to another preferred subject of the present invention, said material of plant origin can be functionalized can be functionalized by opening anhydrides, functionalized or not, generated in situ or prepared beforehand, preferably cyclic carboxylic anhydrides with five centers, preferably the succinic anhydride, aconitic and itaconic anhydrides, with a polyacid by autocatalysis, preferably citric acid, succinic acid, maleic acid, introduced in a nonaqueous medium, preferably aprotic, such as ethyl acetate .
    According to another preferred object of the present invention, said sufficient quantity of material of plant origin is from 0.5 g to 20 g / L to depollute industrial effluents containing concentrations of metal or metals in ionic form from 5 to 500 mg / L, the said metal or metals in ionic form being chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce).
    DESCRIPTION OF THE FIGURES
    FIGURE 1 represents a comparison of the infrared spectra of the bands at 1654 / 1601-15101426 cm ' 1 and 1645 / 1525-1443-1414 cm' 1 for wheat straw and coffee grounds.
    EXPERIMENTAL PART:
    Recycling of eco-materials
    The metallic elements can be in cationic, neutral or anionic form. A heterogeneous catalyst such as Pd / C can be treated by the process. Organometallic catalysts and homogeneous catalysts are also recyclable. The performances are different, but the results are surprising given their generality.
    Example 1: Recycling of palladium (Pd)
    Example 1.1: Study of the variation in Pd in different quantities of dehydrated and ground root extracts of water hyacinths put in a 14 mg / L solution of Pd at pH = 2.5-3.
    Root extracts are heat treated before analysis (550 ° C)
    Label variable Pd Initial concentration mg / L 14.25 Root extract after biosorption (E.R.)1 g / L, 0.5 h % mass 2038 E.R.1 g / L, 2 h % mass 23.76 E.R.1.5 g / L, 0.5 h % mass 15.19 E.R.1.5 g / L, 2 h % mass 17.74 E.R.2 g / L, 0.5 h % mass 11.99
    E.R.2 g / L, 2 h % mass 13.88
    Example 1.2: Study of the quantity of Pd remaining in the effluent after biosorption by different quantities of root extracts of water hyacinths put in a solution at 14 mg / L in Pd, at a pH of 2.5-3 and with a biomass / effluent volume ratio of 0.2g / 0.2L (see table above).
    Label variable Pd Processed solution1 g / L, 0.5 h mg / L 2.09 Processed solution1 g / L, 2 h mg / L 1.59 Processed solution1.5 g / L, 0.5 h mg / L 1.51 Processed solution1.5 g / L, 2 h mg / L 0.01 Processed solution2 g / L, 0.5 h mg / L 0.04 Processed solution2 g / L, 2 h mg / L 0
    Root extracts allow total decontamination of effluents to be achieved, which is not the case with rhizofiltration using live plants, the results of which are presented below for comparative purposes.
    Example 1.3: Rhizofiltration using roots of living feet (1.5 g) on a solution of 200 ml 10 to 14 mg / L of Pd and study of the variation in elements over time in the root extracts and in the solution
    Label variable Pd Initial solutiont = 0 mg / L 14.18 Processed solution0.5 h mg / L 8.49 Processed solution2h mg / L 4.74
    Roots0.5 h % mass 7.64 Roots2h % mass 21.44
    Example 1.4: Comparison of Pd biosorption between different parts of water hyacinths and different operating conditions
    The process is optimized by the use of dehydrated root extracts (without aerial part) and by using the ends of the roots (without stems) as the results in the table below show (the element rates are in mg / L for the initial effluent and in% by mass for the rest of the results, the biomass / volume of effluent ratio is at least 1 g / L):
    Label variable Pd Initial effluent mg / L 14 Effluent after biosorptionusing whole dry hyacinth (5 g / L) mg / L 5.19 Extract of the whole Hyacinth residual afterbiosorption (5 g / L) % mass 1.47 Effluent after biosorption usingfresh wrung roots (5 g / L) mg / L 3.90 Root extract of fresh wrung rootsafter biosorption (5 g / L) % mass 2.39 Effluent after biosorption usingunmilled and dehydrated roots (1 g / L) mg / L 7.70 Root extractunmilled and dehydrated after biosorption (1 g / L) % mass 13.90 Effluent after biosorption using roots offresh unmilled hyacinths (1 g / L) mg / L 6.70 Root extract derived from fresh hyacinthsnot crushed after biosorption (1 g / L) % mass 6.60 Effluent after biosorption using rootsunmilled and air dried (1 g / L) mg / L 3.93 Root extract from unground roots andair dried after biosorption (1 g / L) % mass 12.62
    Effluent after biosorption usinghyacinth stems (without small roots) (1 g / L) mg / L 8.33 Extract derived fromroot stems after biosorption (1 g / L) % mass 3.64 Extract derived from small roots (without stem) afterbiosorption (1 g / L) % mass 21.87 Effluent after biosorption usingsmall roots (without stem) (1 g / L) mg / L 0.91 Effluent after biosorption usingHyacinth root powder (1 g / L) mg / L 539
    Example 1.5: Comparison of Pd biosorption of other eco-materials
    Other crude eco-materials rich in phenolic acids (wheat straw) and lignin have been tested for comparative purposes. The results obtained are shown in the table below (the element rates are in mg / L for the initial effluent and in% by mass for the rest of the results):
    Label variable Pd Initial effluent mg / L mg / L 14.51 Effluent after biosorption(wheat straw powder 5g / L) mg / L 3.38 Wheat straw extractafter biosorption % mass 2.96 Effluent after biosorption (ligninderived from wheat straw 1 g / L) mg / L 1.63 Lignin extractafter biosorption % mass 6.67 Effluent after extractionHeat treated lignin 1 g / L mg / L 1.61 Processed Lignin Extractthermally after biosorption lg / L % mass 3.26 Effluent after biosorption (powder ofpine cone) lg / L) mg / L 1.09 Effluent after biosorption (powder ofwater lettuce root lg / L) mg / L 0.96 Effluent after biosorption (cellulose mg / L 11.8
    Ig / L) Effluent after biosorption (powder ofgreen algae lg / L) mg / L 9.1
    The% of Pd fixed is lower than that of the powder of dehydrated hyacinth roots. However, the heat treatment adopted does not completely destroy the lignin, unlike cellulose. The "catalytic activity" part is the decisive parameter allowing to appreciate the interest of these biosorbent eco-materials.
    The use of a biosorbent of different composition (tannins instead of phenolic polymers) is a complementary solution. It leads to catalysts of more conventional composition, namely monometallic. This possibility is illustrated with coffee grounds as a biosorbent.
    Label Coffee mass / L variable Pd Initial effluent - mg / L 14.46 Effluent after 1 biosorption lg / L mg / L 12.03 Ashes after biosorption - % mass 50.81 Effluent after biosorption 5g / L mg / L 5.03 Ashes after biosorption - % mass 36.50 Effluent after biosorption 5 g / L mg / L 1.05 Washed coffee grounds3 times in the waterEffluent after biosorption 5g / L mg / L 0.72 Ashes after biosorption - % mass 59.48
    Coffee grounds have remarkable Pd chelating properties. Very high biosorption rates can be achieved with 5g / L of coffee grounds. Its heat treatment leads to a metallic catalyst where Pd is the main element. Its metallic composition is different from that derived from the roots of aquatic and terrestrial plants. In the case of tannins such as coffee grounds, heat treatment leads to an almost total destruction of organic matter.
    The results obtained with powders derived from pine cones and roots of water lettuce are spectacular: all the Pd is extracted with lg of biomaterial, without prior functionalization.
    Conc Initial, mg / L AT B 14 1 1
    Example 2 Recycling of Manganese (Mn) and Iron (Fe)
    Fe and Mn constitute the metallic elements of the chemistry of the future. The first is very abundant, inexpensive and non-toxic. Its catalytic properties are broad: oxidations, Lewis acids and coupling agents. The Μη (II, III, IV) constitutes an oxidizing agent which can advantageously replace the reagents and catalysts put in default by the REACH regulation.
    Their recycling is rarely mentioned. However, the discharge of effluents loaded with these metallic species constitutes an environmental problem. Furthermore, according to PIPAME, the known and exploitable resources of Mn could be exhausted in about 40 years. Recycling is therefore useful and necessary. It also opens up new opportunities in synthesis, as shown by the examples presented.
    Industrial environments with significant Fe / Μη contents were treated with root extracts of dehydrated and ground water hyacinths. These roots are then heat treated at 500 ° C. Once the mineralization has been carried out, the analyzes are carried out in ICPMS. With lg / L of biomass, it is possible to extract more than 95% of iron. The results are summarized in the table below and illustrate the possibility of a selective extraction of Fe in the presence of Mn.
    Label variable N / A Mg Al K It Mn Fe Effluentinitial mg / L 13 123 41 2.8 155 9 6.2 Effluentafterbiosorption mg / L 16 107 34 8 148 7 0.3 Extractroot PPm 68848 37871 25342 98207 25342 2288 55790 Extractroot % mass 6.88 3.79 2.53 9.82 2.53 0.23 5.58
    Concerning the calcined root extracts, the accumulation of Mn is low (0.23%). For iron, the quantity is more significant (5.58%), the proportions in the ashes are therefore consistent with the very low concentration of metals remaining in the effluent (0.6%). Biosorption is therefore very effective. The amount of aluminum in the ash is not negligible (3.2% for the concentrated effluent and 2.5% for the untreated) because this element has very interesting properties when it is in the form of aluminum chloride (A1C1 3 ). It is a powerful Lewis acid which has numerous applications in the chemical industry, in particular as a catalyst for the reactions of aromatic electrophilic substitutions.
    A detailed study of the biosorption conditions shows that it is possible to extract the two elements Fe and Mn, by increasing the duration of the biosorption or the quantity of biomass. With 20g / L of biomass (hyacinth root powder), aluminum, zinc and nickel are also fully adsorbed.
    variable Al It Mg Mn Fe Zn Or Initial effluent mg / L 44.5 214 175 13.25 11.14 3.4 2.1 Effluent after biosorption mg / L 0 209.1 134.47 0.82 0.29 0 0
    In conclusion, the powder of hyacinth roots used under the conditions described makes it possible to simultaneously adsorb Fe, Al, Zn and Ni and Mn. It is also possible to sequentially biosorb Fe, Al, Zn, Ni, then Mn.
    Ni recycling
    The biosorption of Ni is an important example. Many countries are exposed to nickel water pollution.
    For example, the absorption was carried out on the effluent consisting of NiSO 4 (15 mg / L of Ni). The absorption is carried out with pine cone powder and water lettuce root powder, which have proven to be the most effective without chemical modification.
    Conc Initial, mg / L AT B 15 1 1
    Nickel extraction with pine cone powder (A) and water lettuce root powder (B)
    Functionalization of eco-materials
    The affinity of transition metals for phenolic biomaterials varies depending on the chemical structure of the cation to be complexed. For example, the affinity of palladium (Pd) for hyacinth powder, water lettuce and pine cone is exceptional. The situation is very different with ruthenium (Ru), iridum or nickel (Ni). Thus, other tests have been carried out after functionalization of the biomaterials, in order to increase the affinity of this type of cations for the biosorbent. This approach is innovative because it leads to recovering plant waste in an original way. The example of lignin is striking: many research works are devoted to the depolymerization of lignin and the production of small aromatic molecules. The objective is based on a new type of recovery of lignin: its use as an eco-support material for recycling organic synthesis catalysts and cleaning up effluents.
    The functionalization of natural phenolic acids is based on the principles of phenol chemistry and acid derivative functions adapted to that of polymers.
    The first mode of functionalization is based on the nucleophilia of phenolic nuclei allowing Mannich-type reactions (example: Betti reaction), diazo coupling, innovative nitration and thiocynanation reactions.
    A second major mode of functionalization has been envisaged: it is based on a carboxylation reaction of the hydroxyl functions making it possible to introduce an ester link functionalized or not. Many examples of the literature describe the enrichment of plant origin materials through the use of citric acid. The process described consists in impregnating the material in water, heating to 60 ° C., then to 100 ° C. until the medium is concentrated, then heating to 120 ° C. to cause the esterification of the hydroxyl functions of the material via the formation. citric anhydride intermediate (B. Zhu et al., J. Hazard. Mater. 153 (2008) 300-308). The process suffers from several limitations: the elimination of water is difficult and unfavorable for the formation of an anhydride; the decomposition of citric acid takes place at a higher temperature (150 ° -170 ° C: Journal of Thermal Analysis and Calorimetry, 2011, Volume 104, Issue 2, pp 731-73) and the formation of citric anhydride is a minority product of the thermal decomposition of citric acid (Biomacromolecules 2007, 8, 3860-3870). The processes described here overcome these limits by replacing water with green solavnts easier to remove (alcohols, ideally ethyl acetate), by controlling beforehand the formation of carboxylic anhydrides and allowing a high degree of functionalization of materials of plant origin. Acid anhydrides are functionalized or not. They can be cylindrical or aliphatic. They allow the introduction of carboxylic acid, sulfonic, phosphonic, carboxylic ester and amide functions under more effective conditions. Direct esterification reactions by autocatalysis (without passing through an intermediate anhydride) are also possible, but again water is to be avoided.
    Example 5: Mannich reaction
    An example of the functionalization of polyphenolic biosorbents is the Mannich reaction.
    Example 5.1; General protocol for the Mannich reaction with the biosorbent (lignin or coffee grounds);
    The paraformaldehyde (500 mmol) is suspended in H 2 O (34 mL) under argon. H3PO4 acid (IN, 1.7 mL) is added and the mixture is stirred at 90 ° C until a clear colorless solution is obtained. The paraformaldehyde solution obtained (13.7 mL) is added dropwise to the mixture of biosorbent (2.35 g), pyrrolidine 137 mmol; 5.5 equiv.) And acetic acid (25 mL) in dioxane (13.7 mL) under argon at room temperature. The reaction is stirred overnight at 50 ° C, then cooled and filtered through filter paper. The solid is washed with dioxane (3 x 30 mL), with water (3 x 30 mL) and with ethanol (3 x 30 mL). The solid is placed in an oven at 80 ° C overnight.
    This possibility of functionalization is very interesting, because it makes it possible to enrich the biosorbents in a nitrogenous group whose chelating capacities are important. This strategy is illustrated with Betti's reaction to the coffee grounds.
    Coffee grounds
    T / /
    Coffee grounds + nR-NH 2 + nR'-CO - R N v-R ')
    Example 5.2: Functionalization by Betti reaction
    Label Amine / amide Aldehyde AT Aniline 2-formylpyridine B Ethylene diamine Benzaldehyde VS Urea Benzaldehyde D Nicotinamide Benzaldehyde E Aniline 4- (dimethylamino) benzaldehyde F Aniline Benzaldehyde
    Procedure:
    0.94 g of water-washed coffee grounds (3 x 100 mL) are added to a solution of amine or amide (10 mmol), of aldehyde (20 mmol) in toluene (10 mL). The mixture is stirred at reflux for 3 h, then cooled and filtered through a paper filter, washed with toluene (3 x 20 mL) and ethanol (3 x 20 mL). The solid is dried in the oven at 85 ° C overnight.
    Biosorption procedure:
    0.5 g of modified coffee grounds are added to 500 mL of Pd (NH 3 ) 4 (NO3) 2 solution (containing 14 mg of Pd / L). The mixture is stirred for 2 h then filtered through a filter paper. The solid is dried in the oven at 85 ° C overnight. The dry solid obtained is then heat treated at 550 ° C for 6 h to obtain the ash enriched with palladium.
    The degree of functionalization is estimated by C / N analyzes.
    Last name %NOT %VS White 0.00 0.00 Atropine (control) 4.86 70.62 Non-coffee grounds 1.80 51.24 functionalized AT 2.66 48.89 B - 3.27 49.45 VS 10.40 49.57 D 2.67 49.45 E 2.49 49.42 F 2.21 49.37
    The effluent decontamination data clearly show the advantage of direct functionalization of biosorbents making it possible to strengthen the chelation of catalytic metallic species. This result is illustrated with lg / L of coffee grounds whose initial effluent is loaded with 14.51 mg / L of Pd:
    Label variable Pd Initial effluent mg / L 14.51 Non-coffee grounds mg / L 12.03 functionalized AT mg / L 7.61 B mg / L 4.85 VS mg / L 4.83 D mg / L 5.08 E mg / L 3.57 F mg / L 4.51
    EXAMPLES 6 Carboxylation
    The direct esterification reactions were carried out by autocatalysis using polyacids, functionalized or not and preferably in a non-aqueous medium. The most effective reactant-catalysts have the following general formula:
    HOOC
    n = 0, 1, 2; R = H, OH, NH 2 , alkyl, aryl, CH 2 SR '”, R' = H, COOH, COOR, CH 2 COOH, NHalkyle, NH-aryle, NAr 2 , NH 2 , OH, R” = H , OH, NH-alkyl, NH-aryl, NAr 2 , NH 2
    HOOC
    n = 0, 1, 2; X = O, NR (R = H, OH, alkyl, aryl), R '= H, COOH, COOR, CH 2 COOH, NH-alkyl, 10 NH-aryl, NAr 2 , NH 2 , OH, R ”= H, OH, NH-alkyl, NH-aryl, NAr 2 , NH 2 .
    The functionalization of the plant material is also carried out with acid anhydrides previously prepared or generated in situ at a temperature greater than or equal to 150 ° C.
    n = 1, 2; R = H, OH, NH 3 + , NR3 + , alkyl, aryl, P (O) OR'2, S (O) OR ' 2 , R' = H, OH, NH 3 + , NR3 + , alkyl, aryl , P (O) OR'2, S (O) OR ' 2

    η = 1, 2; R = H, OH, NH 3 + , NR3 + , alkyl, aryl, P (O) OR'2, S (O) OR ' 2 , R' = H, OH, NH 3 + , NR3 + , alkyl, aryl , P (O) OR'2, S (O) OR ' 2 .
    η = 1, 2; X = O, NR ”’ (R ”’ = H, OH, alkyl, aryl), R ’= H, R” = H, OH.
    n = 1,2,3,4; R = N T R 3 , P (O) OR ' 2 , S (O) OR' 2
    Examples 8.1: Carboxylation via a previously prepared anhydride: example of succinic acid
    3.2 g of succinic anhydride are dissolved in 34 mL of ethyl acetate. The mixture is brought to reflux until the anhydride is completely dissolved, then 5 g of biomass are added to the solution. The suspension is stirred at reflux for 1 hour. The solvent is evaporated under reduced pressure and the solid is left at 120 ° C for 1 night. After cooling to room temperature, 50 mL of distilled water is added to the solid and stirred for 15 min. The mixture is filtered and washed several times with distilled water (200 ml of distilled water for each wash, shaking 15 min before filtration) until neutral pH. The solid is recovered and dried at 85 ° C for 1 night. Then, the functionalized material is suspended in 100 ml of distilled water and 2M NaOH is added until neutral pH. The solution is filtered and washed several times with distilled water until the colorless filtrate is obtained. The solid is dried at around 85 ° C.
    Examples 8.2: Carboxylation by direct esterification and autocatalysis: example of citric acid g of biomass are added to a flask with 4 g of citric acid in 20 ml of anhydrous ethanol. The mixture is stirred for 1 hour at reflux. The solvent is evaporated under reduced pressure and the solid is placed in the oven at 120 ° C for 1 night. After cooling to room temperature, 50 mL of distilled water is added to the solid and stirred for 15 min. The mixture is filtered and washed several times with distilled water (200 ml of distilled water for each wash, shaking 15 min before filtration) until neutral pH. The solid is recovered and placed in the oven at 85 ° C for 1 night. Then, the functionalized biomass is suspended in 100 ml of distilled water and the 2M NaOH is added until neutral pH. The solution is filtered and washed several times with distilled water until the colorless filtrate is obtained. The solid is placed in the oven at 85 ° C.
    Examples 83: Carboxylation using lemon juice 1 g of washed coffee grounds is added to 25 mL of freshly squeezed lemon juice. The reaction mixture is gradually heated to 100 ° C and held until the dry solid is obtained. The product is dried at 120 ° C overnight. Then the solid is washed several times (up to pH 6-7) with distilled water. After having washed the biosorbent with water, NaOH 2M is added until pH = 7, the solid is filtered and washed several times (until neutral pH) with water. The functionalized biosorbent is dried at 85 ° C for 12 h, then analyzed by IR. The grafting rate is high, but lower than that obtained by isolated citric acid.
    EXAMPLE 9 Esterification Using a Simple Alcohol
    The esterification of the COOH groups of the plant-based biosorbent can be carried out with a simple aliphatic alcohol such as methanol, ethanol.
    Hyacinth root powder (5 g) is suspended in methanol (250 mL), acidified with an acid such as H2SO4 conc acid (1 mL). The reaction mixture is heated at reflux for 12 h, then filtered at room temperature. The solid is washed several times with water (up to neutral pH). The functionalized biosorbent is dried at 85 ° C for 12 hours.
    Example 10: Saponification
    Many biosorbents rich in phenolic acid have carboxylic ester functions. In order to increase the number of carboylic functions, a controlled hydrolysis of the ester functions is possible.
    Procedure
    10 g of pine cones powder are dissolved in 60 ml of 0.1 l aqueous sodium hydroxide. The suspension is stirred for 4 hours at 80 ° C, then cooled to room temperature, filtered, washed with water until it returns to neutral, and dried at 85 ° C.
    Example 11. Transfunctionalization
    Certain phenolic biomaterials are naturally rich in carboxylic ester function. This is for example green tea. This property can be exploited to transesterify or transfunctionalize the ester groups with ester groups or polyfontional amides in order to strengthen the affinity of the platinoids for biosorbents. Amines, alcohols, aminosulfonates, aminophosphonates and amino alcohols have been studied.
    Example 11.1.
    Green tea powder previously washed in hot water (1 g) is suspended in ethanolamine at 110 ° C (10 mL). The reaction mixture is heated at reflux for 6 h, then filtered at room temperature. The solid is washed several times with water. The functionalized biosorbent is dried at 85 ° C for 12 hours.
    Example 11.2.
    Green tea powder (1 g), previously washed with hot water, is suspended in the tert-butanol and taurine mixture (lg) at 110 ° C (35 mL). The reaction mixture is heated at reflux for 6 h, then filtered at room temperature. The solid is washed several times with water. The functionalized biosorbent is dried at 85 ° C for 12 hours.
    Example 11.3.
    Green tea powder (400 mg) previously washed in hot water is suspended in 2-dipicolylamine (4 mL) at 110 ° C (35 mL). The reaction mixture is heated at reflux for 6 h, then filtered at room temperature. The solid is washed several times with water. The functionalized biosorbent is dried at 85 ° C for 12 hours.
    Example 12. Recycling Pd with Functionalized Biomass
    The functionalizations described above are implemented to optimize the recycling of
    Pd. The different possibilities described above are directly compared.
    Procedure:
    In an aqueous solution containing 14 ppm of Pd (II), 1 g of biomass is added and the mixture is left to stir for 2 hours. The biomass is filtered, dried at 85 ° C for 12 h and calcined at 550 ° C.
    A) Hyacinth powder functionalized by self-catalyzed esterification with citric acid.
    B) Hyacinth powder functionalized by autocatalysed esterification with succinic acid.
    Conc Pd, mg / L Conc. Initial 14 AT 0 B 0
    The modification of the biomass increases the biosorption capacity of palladium. We manage to extract all the palladium from the solution after functionalization. The carboxylation and esterification lead in each case to a total recycling of the Pd.
    This approach can be extended to other biomaterials:
    A) Coffee grounds functionalized by self-catalyzed esterification with citric acid 15 B) Coffee grounds functionalized by self-catalyzed esterification with succinic acid
    Pd, mg / L Conc. initial 14 AT 0 B 0
    The modification of the coffee grounds by the reaction makes it possible to improve the recycling of Pd (II). It is more than doubled in each case. The functionalizations by carboxylation (A, B) are very effective. In the 2 cases described, the extraction of Pd is total.
    The best results with functionalized biomass have been studied with higher palladium concentrations to test the limits of the process:
    A) Biosorption of Pd in different concentrations with the hyacinth powder functionalized by autocatalysed esterification with citric acid / EtOH
    A) (Pd) = 14mg / L
    B) (Pd) = 30mg / L
    C) (Pd) = 44mg / L
    Conc. Initial After biosorption 14 0 30 0 44 1
    From 14 to 44 mg / L of Pd in solution, the extraction of Pd is very effective with only 1 g of functionalized biosorbent. These results are remarkable and prove the interest of the functionalization of the biosorbent.
    B) Biosorption of Pd in different concentrations with the hyacinth powder esterified by methyl alcohol.
    A: (Pd) = 14 mg / L B: (Pd) = 30 mg / L
    Conc. Initial After biosorption 14 0 30 5
    The extraction of palladium with the esterified biomass remains effective. We can accumulate 25 ppm of palladium under these conditions. To be able to transpose the results to an industrial scale, we carried out the extraction in column (and no longer in batch) on a solution of 40 mg / L of Pd with 1 g of biomass (hyacinth powder esterified with acid citric) for 1 liter of effluent.
    Column biosorption procedure:
    g of biomass (hyacinth powder functionalized with citric acid is placed in the column. The synthetic effluent (IL) containing 40 mg of Pd is passed through the column three times. The passage time of 1 L of solution is 35 mins.
    Pd extraction with hyacinth powder functionalized with citric acid
    Pd, mg / L Conc, initial 41 Passage 1 0 Passage 2 0 Passage 3 0
    The complexation of palladium is remarkable. 41 ppm of Pd, ie 100% metal, is fixed on the biomass after the first pass. We can see that a single pass is enough to absorb all the palladium that is not desorbed after a second and even after a third pass.
    Example 13. Ru, b, Ni are naturally present in an ore rich in Pd. Knowing how to selectively bioconcentrate Pd in the presence of these other elements can be very useful. Functionalized phenolic acids make it possible to obtain very good overall yields on a mixture
    B, Ru, b.
    The conditions described in Example 12 are specific to Pd.
    Initial concPd mg / L Final ConcPd mg / L Initial concRu mg / L Final ConcRu mg / L Initial concRu mg / L Final ConcRu mg / L 15 0 15 15 15 15
    Example 14. Recycling of Ni
    Biosorption of Ni is an interesting and useful case. In addition, the toxicity of Ni implies total exbaction, if one wishes to be in accordance with WHO standards relating to the quality of drinking water. This is why the functionalization of biosorbents has been studied.
    The absorption is carried out with different biosorbents (coffee grounds, hyacinth root powder, water lettuce root powder, pine cone powder, green algae for comparative purposes) chemically functionalized.
    Procedure for the biosorption of Ni in batch:
    g of functionalized biosorbent is added to the NiSO 4 .6H 2 O solution (0.063 g / L). The mixture is stirred for 2 h and then filtered. The solid is dried at 85 ° C overnight. The dry solid obtained is then heat treated at 550 ° C for 6 h to obtain the ash enriched with nickel.
    A) Coffee grounds functionalized by self-catalyzed esterification with citric acid (form 5 COONa)
    B) Hyacinth root powder functionalized by self-catalyzed esterification with citric acid (form -COONa)
    C) Non-functionalized green algae
    Label variable Or Initial effluent mg / L 12 AT mg / L 0 B mg / L 0 VS mg / L 3.73
    The functionalization of the biomass leads to the formation of a biosorbent of the “phenolic acid” type which is effective in eliminating traces of Ni in the solution if new carboxylic groups are introduced, in particular in COONa form. For comparison, we carried out the extraction with green algae. This biomaterial is chosen because it is rich in alginic acid which is known to complex nickel well thanks to the carboxylic group and can be compared with biosorbents functionalized with citric acid. On the other hand, we observe the average efficiency of algae due to the solubility of alginic acids in water which causes the passage of the complex in the filtrate. In addition, the mixture is difficult to filter. This result shows the interest of phenolic acids whose carboxylate groups induce a strong complexing power at neutral pH and the carbon structure makes solid materials insoluble in water.
    Study of the different biosorption parameters of Ni
    We have studied the maximum amount of Ni that can be extracted by the different biosorbents according to their mode of functionalization.
    Nature ofthebiomass Conditionofworkedreading mbiomasse mbiomasse(form-COONa V (2M NaOH) / g ofbiomass Rateworksalization(mol(NaOH) / g Concentrationof thesolutionmetalliqeu Capacityofbiosorptio n, mg / g ofbiomass Biomass pH after neutralization!we
    ) ofbiomass) Powderhyacinth root Succinic anhydride + EtOH 5g 4.3g 0.4 mL / g 0.0008mol / g 40 mg / L 29 mg / g 7 Powderhyacinth root Succinic anhydride + AcOEt 5g 4.2g 0.72 mL / g 0,00034mol / g 40 mg / L 32 mg / g 7 Marcs ofcoffee Succinic anhydride + EtOH 5g 4.7g 0.16 mL / g 0,00064mol / g 40 mg / L 22 mg / g 7 Marcs ofcoffee Succinic anhydride + AcOEt 5g 5.1g 0.28 mL / g 0.0014mol / g 40 mg / L 31 mg / g 7 Pine cone Anhydridesuccinic-t-EtOH 5g 3.4g 0.2 mL / g 0.0008mol / g 40 mg / L 21 mg / g 7 Pine cone Succinic anhydride + AcOEt 5g 5.7g 0.88 mL / g 0.0011mol / g 40 mg / L 30 mg / g 7 Pine cone Citric acid + EtOH 5g 5g 0.8 mL / g 0.0016mol / g 40 mg / L 30 mg / g 7 Pine cone Citric acid + H 2 O 5g - - 40 mg / L 25 mg / g 10 Powderhyacinth root Citric acid + H 2 O 5g 94 mg / L 7 Powderhyacinth root Citric acid + EtOH 5g - - - 94 mg / L 55 mg / g 7 Powderhyacinth root Citric acid + EtOH 5g 66 mg / L 48 mg / g 7 Powderroot of Citric acid + 5g 40 mg / L 40 mg / g 7
    hyacinth EtOH Marcs ofcoffee Citric acid + H 2 O 5g - - - 94 mg / L 29 mg / g 7 Marcs ofcoffee Citric acid + EtOH 5g 5g 0.9 mL / g 0.0018mol / g 94 mg / L 38 mg / g 7 Marcs ofcoffee Citric acid + EtOH 5g 5g 0.9 mL / g 0.0018mol / g 40 mg / L 40 mg / g 7 Powderhyacinth root Anhydridesaconiticanditaconic 5g 3.7g 1.04 mL / g 0.0021mol / g 94 mg / L 50 mg / g 7
    Five important parameters are highlighted: the carboxylate and non-carboxylic form, a neutral biosorption pH, the agents and conditions for functionalization, the nature of the eco-materials.
    Biosorbents rich in sodium carboxylate are very effective and can biosorbed up to 55 mg of Ni per lg of biosorbent (case of hyacinth powder esterified with citritic acid in ethanolic medium).
    Unlike the works described in the literature (B. Zhu et al., J. Hazard. Mater. 153 (2008) 300-308), carboxylation with citric acid does not involve the formation of an intermediate anhydride and n is not an oxidation reaction (Leyva-Ramos et al., Sep. Purif. Tech. 45 (2005) 41-49). Preparing this anydride beforehand leads to such a high level of functionalization that the functionalized carbon skeleton becomes soluble in water during biosorption.
    On the other hand, a self-catalyzed esterification reaction, without water, with a polycarboxylic acid whose first acidity has a pKa equal to or less than 4, or the use of an anhydride less rich in carboxylic unit in non-protic medium are effective. Functionalization with succinic, maleic, phthalic anhydrides, diclohexane dicarboxylic, in ethyl acetate leads to very similar results on the three types of biomass studied: hyacinth powder, coffee grounds and pine cones. Likewise, the fusion and controlled thermal decomposition of citric acid into aconitic and itaconic anhydrides at 160 ° C in the presence of water hyacinth root powders also makes it possible to achieve very high carboxylation rates and very good capacity. adsorption of Ni.
    To prove the generality of the nickel extraction process, we carried out the biosorption in a column filled with biomass, and no longer in batch.
    Example 15. Extraction of Ni with the Hyacinth Powder Functionalized with Citric Acid by a Column-Type Process
    Column biosorption procedure:
    10 g of biomass (hyacinth powder functionalized with citric acid) is placed in the column.
    The synthetic effluent (10 L) containing 40 mg / L of Ni is passed twice through the column. The passage time of 10 L of solution is 45 min.
    Ni, mg / L Conc, initial 40 Passage 1 2
    Complexation is always effective, 38 mg of Ni are fixed on the biomass. A single pass is sufficient to absorb 95% of Ni.
    Example 16. Manganese Biosorption
    Plant derivatives rich in phenolic acids are good biosorbents for Mn if they are adequately functionalized. They can be used again in synthetic chemistry, in particular in oxidation reactions.
    MnSO ± biosorption procedure:
    g of hyacinth root powder functionalized with citric acid is added to 1 L of MnSO 4 solution (24 mg / L, at neutral pH). The mixture is stirred for 2 h and then filtered. The solid is dried in the oven at 85 ° C overnight. The dry solid obtained is then heat treated at 550 ° C for 6 h to obtain the ashes enriched with manganese.
    Label variable Mn Initial effluent mg / L 23.44 Effluent after biosorption mg / L 0.4 Ashes % mass 18
    The functionalized biosorbent is very effective in purifying manganese-laden effluents. Thanks to this process, we obtain lower manganese levels than those fixed by regulations.
    To verify the general interest of this result, it was implemented from industrial effluents resulting from the extraction of pyrite, that is to say on with acidic media, rich in Mn, but of polymetallic composition.
    Purification tests of industrial effluents from the pyrite quarry:
    We carried out the purification of effluent from a pyrite quarry with lg of biomass for IL of effluent using two methods: batch and column. The results are just as effective despite the multi-metallic composition of the medium.
    Example 24. Purification of neutral industrial effluent with functionalized biomass (hyacinth powder functionalized with citric acid / EtOH)
    One liter of industrial effluent (pH = 2.5-3.5) is neutralized with sodium hydroxide (NaOH 2M) until neutral pH, then it is eluted on a column containing 1 g of functionalized biomass (root powder of hyacinth functionalized with citric acid). After 1 passage at room temperature (30 minutes), the powder is dried at 85 ° C. The dry residue is calcined at 550 ° C, to obtain a powder enriched with metals.
    We observe a partial depollution of the effluent with 1 g of biomass per liter, because all the metallic elements are biosorbed. To obtain complete purification of the effluent, 8 g of functionalized biosorbent (hyacinth root powder functionalized by self-catalyzed esterification with citric acid per liter of industrial effluent must be used.
    Water hyacinth rootsesterified Pine conesesterified coffee groundsesterified Cone.initialmg / L Conc. final(1 Pass)mg / L Conc.initialmg / L Conc. final(1 Pass)mg / L Conc.initialmg / L Conc. final(1 Pass)mg / L
    Al 18.6 0 4.3 0 2.5 0 Fe 4.4 0.3 8.2 1 3.8 0.3 It 218 208 65.5 14 113 51.5 Mg 179 147 59 16 23 3.0 Or 1.3 0 0.4 0 0 0 Zn 2.5 0 3 0 0.3 0 Mn 11.7 1.7 11.4 1.6 10 1.6
    The purification of the effluent is very effective. Less than 1 ppm of Fe, Al and Mn remains after the first pass on the column. We can see that one pass is sufficient to effectively purify the industrial effluent and have the manganese levels below European standards. Unlike non-functionalized materials, all the metallic elements are retained (Al, Fe, Ni, Zn, Mn) but also Ca and Mg. This result can be generalized to the different types of materials rich in phenolic acids, in particular those which are rich in lignin or tannins.
    Rare earth recycling
    The growing importance and access to the resource are delicate geoeconomic problems. The study of simple and efficient recycling techniques is obvious for various rare earths: Sc, Ce, Yb, Eu ...
    EXAMPLE 17 Extraction of Scandium with Hyacinth Powder Functionalized with Citric Acid
    The hydrated Sc (NO 3 ) 3 (0.072g) is dissolved in 1 L of water. It is very weakly retained by biosorbents such as water hyacinth roots. On the other hand, the biosorbent capacities of Sc are improved after functionalization.
    Initial conc, ppm Conc. final, ppm 26 5
    The carboxylation of the biomaterial premet to obtain an adsorption capacity of 21 mg / L from an initial concetration of 26 mg / L.
    Example 18. Extraction of Scandium in the Presence of Excess Ni with the Hyacinth Powder Functionalized with Citric Acid
    Scandium is often extracted from other minerals from which it must be separated. This is for example the Ni.
    - Batch process
    To study the capacity of biomass functionalized with citric acid to selectively retain scandium compared to nickel, we prepared a synthetic effluent with concentrations of Sc = 25 mg / L and Ni = 72 mg / L. the separation is carried out in batch.
    We can see the functionalized biomass selectively extracts scandium compared to nickel, even if the latter is in excess. By comparing the result with the extraction of scandium without nickel, we can see that the biomass accumulates around 20 ppm of scandium which is comparable with the test of scandium / nickel mixture or 20 ppm of scandium were fixed and the sites remaining complexing agent fixed nickel without replacing scandium with nickel.
    - Column process
    To mimic the purification transposition of the effluent at the industrial level, we considered purification on a column filled with carboxylated biomass. Knowing that the concentration of scandium in existing ores is very low, we prepared the solution of nickel and scandium with the ratio 112 ppm of Ni for 2 ppm of Sc. The aim is to see if the scandium remains fixed on the column in the presence of a large excess of nickel, which makes it possible to enrich the biomass with scandium after several effluent passages with a low concentration of scandium.
    0.6 g of biomass (hyacinth powder functionalized with citric acid) is placed in the column. The synthetic effluent (0.6 mL) containing 112 mg / L of Ni and 2.3 mg / L of scandium is passed through the column three times. The residence time is 10 min.
    Nickel, mg / L Scandium, mg / L Column process Conc, initial 112 2.3 Passage 1 68 0 Passage 2 64 0 Passage 3 64 0
    Batch process Conc, initial 72 25 Passage 1 51 4
    The result obtained is spectacular: it shows a rapid, simple, efficient and bio-based process which makes it possible to purify the industrial effluent loaded with nickel and scandium and at the same time preferentially extract scandium. Π is a new method for enriching biomass with this rare and precious metal.
    It should be noted that scandium and nickel remain fixed on the biomass and are not eluted even after the third pass. So a single pass over a column is sufficient. Passages 2 and 3 show that there is no desorption.
    Complexation with biomass is easily extensible to other rare earths such as Ce, Yb 10 and Eu.
    Example 19. Recycling of Ce
    Complexation with biomass is easily extendable to other rare earths such as Ce. A solution of cerium at a concentration of 32 ppm was prepared. The extraction was carried out with hyacinth root powder functionalized with citric acid.
    Extraction of cerium with hyacinth powder functionalized with citric acid
    Conc, initial, mg / L Conc. final, mg / L Cerium 32 0.8
    Almost all of cerium is complexed by functionalized biomass.
    Example 20. Recycling of Ytterbium
    Biosorption is studied with a catalytic solution of Yb (NO 3 ) 3 pentahydrate at 16 mg / L of ytterbium (Yb) and the results of this analysis are described in the table below. The biosorbent selected is coffee grounds functionalized with citric acid.
    Extraction of Ytterbium with coffee grounds functionalized with citric acid
    Conc, initial, mg / L
    Conc. final, mg / L
    Ytterbium 16 1.0
    Functionalized biomass is capable of concentrating more than 15 mg of Ytterbium.
    Example 21. Recycling of Europium
    Biosorption is studied with a catalytic solution of Eu (NO 3 ) 3 hydrate at 13 mg / L of europium (Eu) and the results of this analysis are described in the table below. The biosorbent selected is coffee grounds functionalized with citric acid.
    Extraction of Ytterbium with coffee grounds functionalized with citric acid
    Conc, initial, mg / L Conc. final, mg / L Europium 13 0
    All of the europium in this concentration is biosorbed with the functionalized biomass.
    Example 22. Cu recycling
    The extraction was carried out with coffee grounds functionalized with citric acid according to the ethanol process.
    The biomass (coffee grounds functionalized with citric acid / EtOH) is put in a solution of Cu (NO 3 ) 2. 3H 2 O for 1 liter of solution. The suspension was stirred at room temperature, then filtered and the solid was dried in the oven at 85 ° C.
    Copper extraction with coffee grounds functionalized with citric acid
    Durationbiosorption Number ofbiomass / L Conc, initialCu, mg / L Conc. finalCu, mg / L Comment 2h 1 g 15 0 The data is greater than that of the binding: Int. J. Approx. Sci. Technol. (2013) 10: 611-622, Cerino-Cordova et al. 2h 1 g 101 54 5 days 2.5g 315 186
    129 mg of copper were accumulated by the biomass in 5 days, which shows a great capacity for extracting functionalized coffee grounds.
    Example 23. Recycling of Pb
    A solution of lead was prepared from Pb (NO 3 ) 2 . The extraction was carried out with coffee grounds functionalized with citric acid / EtOH.
    Lead extraction with coffee grounds functionalized with citric acid
    Durationbiosorption Number ofbiomass / L Conc, initialPb, mg / L Conc. finalPb, mg / L Comment 2h 1 g 15 0 The data is greater than that of the binding: Int. J. Approx. Sci. Technol. (2013) 10: 611-622, Cerino-Cordova et al. 2h 1 g 142 86 5 days 1.25 g 213 46
    lg of biomass extracted 56 mg of lead in 2 hours. 170 mg of lead were accumulated by 1.25 g of biomass in 5 days, which shows a great capacity for extracting lead with functionalized coffee grounds.
    Example 24. Recycling of Cd
    A cadmium solution at a concentration of 15 ppm was prepared from Cd (NO 3 ) 2 * 4H 2 O. The extraction was carried out with 1 g of coffee grounds functionalized with citric acid / EtOH.
    Lead extraction with coffee grounds functionalized with citric acid
    Conc, initial, mg / L Conc. final, mg / L Cadmium 15 0
    All of the cadmium is absorbed by 1 g of biomass in 2 hours.
    Example 25. Coupling reactions
    Recycled catalytic systems are called Phyto-Pd. Their reactivity is illustrated through the important examples of palladium chemistry: reactions of Suzuki and Heck. Examples in heterocyclic series, known for their difficulty are described. Similarly, important industrial targets, such as bixafen and boscalid are chosen to illustrate the high efficiency of the systems.
    Example 25.1: Coupling reaction between heterocyclic brominated derivatives with boronic acids (Suzuki reaction)
    The Suzuki reaction can take place in water, butanol or a mixture of water / glycerol or butanol / glycerol, ie in green solvents.
    B (OH) 2
    Ar
    ArBr
    Boronic acid Bromideheteroarylor aryl Biosorbentused T (h) Solvent Conversion ^^ B (0H) 2 O Powdersroots ofhyacinths 2 Glycerol 92% O Powdersroots ofhyacinths 2 nBuOH 73% Powdersroots ofhyacinths 2 H 2 O / nBuOH (9/1) 85% Q Br N Lignin 2 H 2 0 75% j / ^ / b (oh) 2 Q Br N Powdersroots ofhyacinths 2 h 2 o > 99% (θ / Β (ΟΗ > * Br- ^ ÇKsr Powdersroots ofhyacinths 2 nBuOH 39%(single coupling= 56%decoupling =44%)
    V Powdersroots of 2 Glycerol/ > 99% TCl XX hyacinths nBuOH
    The last example in the table above should be noted, since it corresponds to the synthesis of a key intermediate in bixafen. The reaction is quantitative in two hours, without adding any ligand, phosphine or particular additive. The catalyst is recyclable at the end of the reaction. The Pd is reduced in situ to black Pd by glycerol. It is isolated by filtration, introduced into a solution of IM nitric acid. Functionalized hyacinth powder allows quantitative recovery of the Pd in two. hours and regeneration of Phyto-Pd by the heat treatment / HCl activation sequence. The coffee grounds are just as effective. These results can be advantageously compared to those described in the literature (WO 2015/011032 A1, PCT / EP2014 / 065463) where the process requires a very specific phosphine: ((/ -Bu) 2 PhPH) BF 4 , a ligated Pd: Pd (0.12 mol%), the reaction lasts 13 hours and the catalyst is not recyclable. , The yield is lower eur (86%).
    General experimental protocol for the Suzuki reaction
    Aryl halide (1.25 mmol, 1 equiv.), Phenyl boronic acid (1.3 mmol, 1.1 equiv.), Potassium carbonate (1.5 mmol, 1.2 equiv.) and 0.1 mol% of Pd-based catalyst (Phyto-Pd) are placed in a flask. 2.5 mL of solvent is added and the suspension obtained is placed under argon. The reaction mixture is stirred at 95 ° C for 2 h. After 2 h the mixture is cooled. The product is extracted with ethyl acetate and washed with water. The conversion is determined by GC / MS with dodecane as an internal standard.
    Entry 1 was performed on a 20.4 g 2-bromothiophene scale, ie 111 mg of Phyto-Pd (0.125 mmol of Pd). This is an interesting case of homogeneous catalysis, Phyto-Pd is completely soluble in the coupling solvent. The catalyst was recycled and reused from the catalytic system in the same reaction. The procedure is based on the filtration of the Pd formed at the end of the reaction and placed in the aqueous phase at pH = 2.5 using nitric acid. After stirring for 2 hours, the results obtained are spectacular: 84% of Pd is re-extracted by the powder of water hyacinth roots. After transformation of the root extracts according to the standard process, the catalytic activity of the regenerated Phyto-Pd is retained.
    Mineral composition of solids and solutions used in the recycling of palladium (analyzes
    MP-AES (% mass for solids, in mg / L for liquid phases).
    Liquid phases (mg / L) Pd Aqueous phase resulting from the reaction 0 Organic phase resulting from the reaction 0 Effluent before biosorption 13.2 Effluent after biosorption 0.01 Solid phase (% mass) Pd Phyto-Pd 13.8
    The process can be generalized to other heterocyclic halogenated derivatives in glycerol.
    It is also possible to carry out the transformations with butanol in the case of non-hydrophilic brominated derivatives (bromothiophene) or in water with nitrogenous heterocycles (bromopyridine). The yields are comparable. These reactions are therefore remarkably effective, simple to implement and economical (no ligand, no additive) and completely eco-compatible (green solvents and recyclability of Phyto-Pd.
    Similarly, these catalysts can promote couplings between boronic acids and heterocyclic brominated derivatives. Again, no ligand is needed. Green solvents lead to very good yields.
    + Ar-B (OH) 2 -►
    Boronic acids T (h) Conversion(%) 4 88 ^ 2 ^ B < OH ) 2 s 50 95 (84) ca K0Hh H 4 > 99 (90) c, XX 4 94
    ^ x ^ B (OH) 2 ju 4 99 here ψCl
    It is thus possible to couple two tbiophenes together, which opens access to the conductive compounds.
    The Suzuki reaction in heterocyclic series can also be carried out using Phyto-Pd recycled by biosorption with coffee grounds.
    The reaction is carried out in water with a yield of 97%.
    Experimental protocol for the reaction of Suzuki in water
    3-bromopyridine (4.75 mmol, 1 equiv.), Phenyl boronic acid (5.23 mmol, 1.1 equiv.), Potassium carbonate (5.7 mmol, 1.2 equiv.) And 0 , 1 mol% of catalyst based on Pd (20.1% mass of Pd in the catalyst) are placed in a flask. 9.5 mL of solvent is added and the suspension obtained is placed under argon. The reaction mixture is stirred at 95 ° C for 2 h. After 2 h the mixture is cooled. The product is extracted with ethyl acetate and washed with water. The 97% conversion is determined in GC / MS with dodecane as an internal standard.
    Example 25.2: Reaction of iodobenzene with methyl acrylate (Heck reaction)
    O
    Iodobenzene (1.4 mmol, 1.4 equiv.), Potassium carbonate (1.3 mmol, 1.3 equiv.), 0.5 mol% of Phyto-Pd catalyst (19% mass of Pd in the catalyst ) and methyl acrylate (1 mmol, 1 equiv.) are dissolved in gamma-valerolactone (2 mL) under argon at room temperature. The reaction mixture is heated at 120 ° C for 4 h. After 4 h, the reaction is cooled and analyzed in GC / MS with dodecane as an internal standard. The conversion is complete. 93% of monoadduct are observed and 7% of diadduit.
    The reaction is compared with commercial catalysts like PdCl 2 and Pd (OAc) 2 . The conversion is total in both cases, but the ratio between the monoadduit and the diadduit is
    80/20 and 87/13 respectively. This difference shows that the reaction with Phyto-Pd is more selective compared to the single coupling product.
    Using bromobenzene, only the monoadduct is observed.
    Another Heck reaction, below, shows a much higher percentage of conversion with the bio-based catalyst compared to the commercial catalyst.

    Catalyst Time % conversion Phyto-Pd 15 mins 74 K 2 PdCLt 15 mins 53 Phyto-Pd 30 mins 96 IÇPdCL, 30 mins 82
    Example 25.3: Sonogashira reaction
    With recycled Phyto-Pd, coupling of Sonogashira can be carried out without ligand and without copper salts. The industrial example of the coupling of butyn-3-ol and 4‘-hydroxy-3’-iodo-biphenyl-4carbonitrile illustrates the potential of Phyto-Pd in this type of reaction.
    i
    In 100 ml of a 50/50 glyecrol / butanol mixture, 0.05 mol of iodized derivative, 0.1 mol of butyn-3-ol are added in the presence of 0.1 mol of K2CO3, and of Phyto-Pd derivative water lettuce (0.5 mol% Pd). The reaction medium is heated to 100 ° C. After 4 h, the reaction is cooled and analyzed in GC / MS with dodecane as an internal standard. The conversion is complete.
    This result is particularly interesting because it is a key step in the industrial synthesis of ABT-239, an antagonist of the histamine H3 receptor. It can be advantageously compared with the data in the literature which describe liganded palladium catalysts (example:
    PdCl 2 complex (PPh 3 ) 2) in the presence of copper salts (Cul): Organic Process Research Development 2005, 9 (1), 45-50), which also requires higher amounts of Pd (1 mol% in the previous reference).
    The Sonogashira reaction catalyzed by a Phyto-Pd can be extended to the synthesis of ji-conjugated polymers, such as polyarylene, polyphenylacetylene. Again, copper salts and the introduction of ligands is not helpful. It is a simple and efficient access to the polymers used in OLEDs.
    η X — Ar 1 —X + nH - Ar 2 - = - h
    I Phyto-Pd f-AH - - AT - = -; not
    Example: X = I, Ar '= Ar 2 = Ph
    In 100 ml of a 50/50 glycerol / butanol mixture, 0.1 mol of 1,4-diiodobenzene, 0.1 mol of 1,4diethynylbenzene are added in the presence of 0.1 mol of K 2 CO 3 , and Phyto-Pd derived from pine cone (0.5 mol% Pd). The reaction medium is heated to 100 ° C. After 8 h, the reaction is cooled and analyzed by NMR and IR showing the formation of polycondensation products. With phenylacetylene, the conversion is complete after 2 h of reaction. This result is advantageously compared to that of Yang (J. Org. Chem. 2005, 70, 391-393) which expects 80% yield after 24 h and 1% Pd.
    EXAMPLE 26 Reductive Chemistry of Pd (II)
    Example 26.1: Reduction of an enone with the ashes of Phyto-Pd
    The enone (2.5 mmol, 1 equiv.) And the Phyto-Pd (resulting from the controlled heat treatment of the roots of water hyacinths) (0.15 equiv.) Are suspended under argon in degassed THF (2 mL). Formic acid (5.0 mmol, 2 equiv.) Is added and the resulting mixture is refluxed. At the end of
    3 h, the mixture is filtered through dicalite and concentrated under reduced pressure. A yield of 85% is obtained in ketone. It is important to note that the reaction does not work with Pd oxide. By hardening the conditions (duration, catalytic charge), the percentage of alcohol becomes the majority.
    Example 26.2: Isomerization of an exocycyclic double bond of 2-cyclopentenone
    R = alkyl, H
    Cyclopentenone (Immol; 1 equiv.) Is added to 0.1 mol% of Phyto-Pd catalyst (20% mass of Pd in the catalyst), then the mixture obtained is stirred for 16 h under argon at room temperature. The reaction mixture becomes dark black. After stirring overnight, the composition of the reaction mixture is analyzed in GC / MS. The conversion into a product bearing an endocyclic double bond is 52%.
    Bio-sourced chemistry of iron (Fe):
    Example 27 Oxidation of Alcohols
    Phyto-Fe
    H2O2
    CHO
    Example 27.1: General protocol for the oxidation of benzyl alcohol to aldehyde with Phyto-Fe without ligand:
    Phyto-Fe (20 mmol, 2 mol%) is added to 1 ml of H 2 O and stirred for 20 min to obtain a clear yellow solution. After addition of the benzyl alcohol (1 mmol) the reaction mixture is stirred vigorously, then the H 2 O 2 (30% in water, 2 mmol, 0.2 ml) is added dropwise over 10 min at using a syringe pump at room temperature. The reaction mixture is stirred for 3 h, then the aldehyde is extracted with ethyl acetate and analyzed in GC / MS with dodecane as internal standard. A yield of 35% is obtained.
    Example 27.2: General protocol for the oxidation of benzyl alcohol to aldehyde with Phyto-Fe activated by a diazotized ligand:
    Phyto-Fe (20 mmol, 2 mol%) and ligand (20 mmol, 2 mol%; for example phytophytin) are added to 1 ml of H 2 O. The mixture is stirred for 20 min to obtain a solution clear yellow. After the addition of benzyl alcohol (1 mmol) to the solution, the reaction mixture is stirred vigorously and then H 2 O 2 (30% in water, 2 mmol, 0.2 mL) is added dropwise in 10 min using a syringe pump at room temperature. The reaction mixture is stirred for 3 h, then the aldehyde was extracted with ethyl acetate and analyzed in GC / MS with dodecane as internal standard. A yield of 59% is obtained.
    An innovative recovery of iron was carried out with the biomaterial richest in Fe.
    Label Al It Fe K Mg Mn N / A Zn Root powderhyacinthsPPm 24626 56187 55690 94899 37871 2343 68848 1451 % mass 2.46 5.62 5.57 9.49 3.79 0.23 6.88 0.15
    The root extracts were heat treated at 550 ° C, then activated with 6N HCl at reflux for 6H. After concentrating the reaction medium, the yellow solid obtained, called Phyto-Fe, was tested in unusual SEAr reactions.
    Example 27.3. Oxidative halogenations and unusual SEAr (nitration, thiocyanation)
    NaBr / montmorillonite K10
    Br
    OMe
    A Phyto-Fe comprising 0.05 mole of iron, in the presence of an equimolar amount of sodium (or potassium) bromide and anisole are heated at 80 ° C. overnight in the presence of 200 mg of montmorillonite K10.
    The monobromination product is obtained with a yield of 74%. This result is remarkable, because bromination is possible without dibroma. It is particularly surprising because, from a thermodynamic point of view, Fe (HI) is not sufficiently oxidizing to oxidize bromide to dibroma. It should also be noted that the solid support is not silica, but montmorillonite which does not pose the same toxicity problems.
    This bromination method is unique if we refer to the data in the literature. The table presented below makes it possible to highlight the advantage of the technology presented: they are based on the use of a non-noble catalyst, easy to access, without dangerous co-oxidant, without solvent, without silica and with a direct process and very easy to implement, and using bio-sourced and durable materials. Conventional methods require dibroma (irritant) in the presence of Lewis acids or NBS, which generates a toxic imide. The examples given below are based on the use of NaBr, in the presence of complex catalysts or compounds of noble metals, oxidants and toxic solvents. A comparative bibliographic analysis proves that the proposed method is real progress in the field of Journal of Organic Chemistry, 67 (13), 44874493, 2002; Eut. Pat. Appl. 1138657, 2001; Tetrahedron Letters, 31 (14), 2007-10, 1990; Eur. Pat. Appl., 1138657, 2001; Bulletin of the Korean Chemical Society, 23 (5), 773-775, 2002; Synthetic communications, 31 (19), 2995-2963, 2001; Journal of Chemical Research, (6), 366-368, 2006; Huaxue Yu Shengwu Gongcheng, 29 (11), 47-49, 2012; Catalysis Science & Technology, 5 (10), 4778-4789, 2015; Journal of Molecular catalaysis A: Chemical, 371, 56-62, 2013; Chemical, 371, 56-62, 2013 ChemSusChem 6 (8) 1337-1340, 2013; Catalysis Letters, 137 (3-4), 190-201, 2010; Green Chemistry, 8 (10), 916-922, 2006; Synthetic communications, 28 (8), 1463-1470, 1998; Synthesis (2), 221-223, 2006; Tetrahedron letters, 44 (49), 8781-8785, 2003; e-EROS Encycl. of Reagents for Organic Synthesis 1-9, 2006; Advanced Synthesis & Catalysis, 351 (11 + 12), 19251932,2009).
    It should be noted that it is possible to extend the concept to chlorination reactions, but especially of iodization in aromatic series. So, for example, the method allows tri-iodination of aniline or iodization of Tanisole or thiophene.
    The aromatic derivative (0.1 mmol; 1 eq), Phyto-Fe (0.105 g (5.3% Iron; 0.1 mmol; 1 eq)), Nal 5 (0.1 mmol; 1 eq) and the montmorillonite K10 (0.2 g) are mixed and stirred at 80 ° C for 24 hours. At the end of the reaction, the mixture is cooled to room temperature, washed with dichloromethane and analyzed in GC-MS, then in NMR.
    Label Conv% Anisole 65% Thiophene 64%
    The process can also be extended to other salts, such as KSCN, KNO 3 , and therefore allow thiocyanation or direct nitration under very mild conditions.
    Label Conv% KSCN 61% kno 3 83% (79% yield)
    EXAMPLE 28 Biosourced Chemistry of Zinc (Zn)
    Phyto-Zn is prepared by adding one gram of water hyacinth root extract to 100 mL of a 10 mg / L Zn solution. After 2 hours of stirring, the powder is filtered, dried and treated at 550 ° C.
    Example 28.1: Condensation reaction of a carbanion on a carbonyl compound (Doebner-Knoevenagel type reaction)
    Phyto-Zn recovered by recycling has interesting Lewis acid properties. The formation of C-C bonds by Doebner-Knoevenagel type reaction is an interesting example. It is involved in the synthesis of many compounds of interest such as atorvastatin, the active principle of a cholesterol-lowering drug from Pfizer known as Tahor in France or Lipitor in the United States, or imiquimod, a principle active ingredient of Aldara and Zyclara, drugs that modify the immune response and are used to treat skin conditions. Conventional reaction conditions involve the use of solvents and a base in a stoichiometric amount.
    Synthesis of imiquimod
    The use of green solvents or even the absence of solvent and the use of heterogeneous catalysis are two possible ways to make this reaction greener. The catalytic activity of zinc chloride, a Lewis acid catalyst, in the absence of solvent has been demonstrated for the reaction of
    Knoevenagel. However, zinc chloride is a very hygroscopic compound, difficult to handle and it is a homogeneous catalysis.
    , CHO
    Phyto-Zn
    RL, R 2
    Without nucleophilic solvent 100 ° C
    R2
    R 1
    Catalyst Malononitrile Cyanoacetatemethyl Acetylacetone Acetoacetateethyl - 0% 0% 0% 0% Phyto-Zn 97% 33% 51% 53% K 2 ZnCl4 82% 44% <5% 0%
    These results prove the interest of this recycling technique. It leads to a Phyto-Zn whose activity is at least equal to or even greater than K 2 ZnCl 4> zinc salt present in the Phyto-Zn.
    Experimental protocol for the Knoevenasel reaction
    In a reactor, Phyto-Zn (0.06 g; 5mol% in Zn), previously heat treated for 5 min at 150 ° C., is introduced with benzaldehyde (5 mmol, 1 equiv.) And malononitrile (5 mmol, 1 equiv.) At room temperature. Then the reaction mixture is heated at 100 ° C for 1 h. The solution is cooled, then the product formed is extracted with ethyl acetate. The conversion is established by
    GC / MS with biphenyl as an internal standard. It is 97% additive to Knoevenagel.
    EXAMPLE 29 Biosourced Chemistry of Nickel (Ni)
    The biosorbent loaded with Ni is useful in organic synthesis. It is for example a good coupling reaction catalyst, such as the Suzuki reaction.
    Procedure for the Suzuki reaction g of ashes derived from functionalized water hyacinths and treated at 550 ° C. are diluted in 15 ml of formic acid. The solution is brought to reflux. The solution gradually turns from black to green, reflecting the formation of nickel formate. After 7 hours, the medium is cooled, filtered, the solid is washed with formic acid, then with water. It is redissolved in hot to hot water and the medium is evaporated under reduced pressure. It is dried, then engaged in reaction to Suzuki.
    The eco-formate of Ni is dissolved in a glycerol / BuOH mixture (1/1 by volume) in the presence of two equivalents of potassium carbonate, of 1.2 equivalents of boronic acid and of one equivalent of iodobenzene. The mixture is brought to 120 ° C for 8 hours. 80% of coupling product are then observed by GC MS analysis with respect to the internal reference (dodecane).
    Example 30. Biosourced Chemistry of Rare Earths
    The powder bursting with cerium was calcined and valued in the Biginelli reaction.
    Procedure for preparing Phyto-Ce:
    mg of ash enriched with cerium (25% of cerium) are diluted in 15 mL of 6N HCl acid and heated under reflux for 6 hours. Then cooled to room temperature, filtered and concentrated under reduced pressure. A hygroscopic yellow powder is obtained with a mass of 42 mg.
    Procedure for the Biginelli reaction:
    The solution of ethyl acetoacetate (0.013 g; 0.1 mol), 4-methoxybenzaldehyde (0.014 g; 0.1 mmol) and urea (0.018 g; 0.3 mol) in ethanol (0.05 mL) is heated to reflux in the presence of Phyto-Ce (0.037 g; 0.025 mol) for 2 h 30 min. Part of the solution is withdrawn, centrifuged and the liquid is passed through the GCMS. The 93% conversion is observed after 2 h 30 min.
    Ο
    Biginelli reaction with a Phyto-Ce
    Example 31. Epoxidation with the ash from the extraction of Mn using the powder of water hyacinth roots
    The epoxidation of alkenes can also be easily carried out from the ashes resulting from the extraction of Mn using the powder of water hyacinth roots in the presence of a co-oxidant such as hydrogen peroxide. The method can be advantageously compared to the methods of the literature. The process is simple since it is a direct recovery of the ashes. No activation has been performed.
    Substrate Phyto-Mn: Ashes Phyto-Mn: EcoMn Styrene 100% 91% Limonene 79%(of which 93% di-epoxide) 50%(100% monoepoxide)
    The easy obtaining of limonene di-epoxide is very interesting, because it is a molecule which can replace epichlorohydrin, without having the disadvantages of its toxicity.
    General operating mode:
    NaHCO 3 (1.5 g; 18 mmol; 5 eq), the ashes enriched in Mn derived from the powder of water hyacinth roots (0.071 g; 0.02 mmol; 0.005 eq of Mn; Mn in the ashes = 1.79%), the DMF / H 2 O mixture (1/1) (3.3 mL) and styrene (0.413 mL; 3.6 mmol; 1 eq) are added to a 25 mL flask at 30 ° C to air. After 10 minutes of stirring, 30% H 2 O 2 (3.3 mL; 36 mmol; 10 eq) is added dropwise over 2 hours to the reaction mixture at 30 ° C in air. Stirring is continued for a further min, then the reaction is cooled to room temperature. The product is extracted with dichloromethane and analyzed in GC MS.
    权利要求:
    Claims (25)
    [1" id="c-fr-0001]
    Claims
    1. Process for the preparation of a material of plant origin rich in phenolic acids and having fixed at least one metal, said process comprising bringing an effluent containing metal cations into contact, and for example an effluent contaminated with platinoids , with a material of plant origin which is no longer a complete living plant, but for example plant roots, crushed and dried in the form of a powder.
    [2" id="c-fr-0002]
    2. Method for recycling metallic catalysts, in particular metallic catalysts comprising at least one metal chosen in particular from platinum (Pt), palladium (Pd), rhodium (Rh) and more particularly palladium (Pd), said method being characterized in that a reaction medium in which a chemical reaction using said metal catalyst has been carried out or an effluent from a reaction medium in which a chemical reaction using said metal catalyst has been carried out is treated with a reaction material plant origin in the form of a powder insoluble in water rich in phenolic acids, and optionally subjected to an acid or basic treatment, the ash obtained by heat treatment of said material of plant origin rich in phenolic acids, having fixed the metal constituting the metal catalyst comprising at least one metal chosen in particular from platinum (Pt), the palladium (Pd), rhodium (Rh) and more particularly palladium (Pd) and thus obtains the recycled catalyst.
    [3" id="c-fr-0003]
    3. Process for the preparation of a material of plant origin having fixed at least one metal, characterized in that it comprises the following steps:
    adding a material of plant origin in the form of a powder insoluble in water, in an amount sufficient to fix said at least one metal, in an aqueous liquid medium containing at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru ), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg ), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb) , cerium (Ce),
    -allow said insoluble powder to act in said aqueous liquid medium containing at least one of said metal for at least one hour, preferably between 1 and 2 hours or at least 2 hours,
    -filtering said aqueous medium to recover said powder having fixed at least 90%, preferably 100% of said metal present in said aqueous liquid medium.
    [4" id="c-fr-0004]
    4. Method according to any of claims 1 to 3, characterized in that the plant material is chosen from:
    the polymeric structures constituting the roots of certain aquatic plants, such as: roots of water hyacinths or water lettuces; tannins, such as: coffee or tea grounds;
    natural materials rich in lignin, such as wheat straw, pine cones, coconut fill.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, in which the material of plant origin comprises phenolic acid functions and is capable of fixing more than 90%, preferably more than 95%, preferably more than 99% by weight. '' at least one metal included in an effluent.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which the metal is chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (b), rhodium (Rb), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce).
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, in which the material of plant origin rich in phenolic acids is a material of plant origin for which the intensity of said bands characteristic of the valence vibration of (C = O) of carboxylic acids is greater than the intensity of said bands characteristic of the valence vibration of the aromatic cycle, determined on the basis of their infrared spectral data.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, in which the phenolic acids contained in said material of plant origin have been functionalized before fixing at least one metal.
    [9" id="c-fr-0009]
    9. The method of claim 8, wherein the functionalization of said phenolic acids is carried out by a Mannich type reaction such as the Betti reaction, by a reaction of coupling of the diazo, by a cross-functionalization reaction such as the passage of ester to an amide, the use of amino residues such as dipicolylamine to introduce nitrogenous ligends, by the use of amino residues for the introduction of a sulphonic group by addition to propane sulphone, by the direct use of taurine, by oxidation of said amino residues such as the oxidation of the pyridine nucleus to pyridine oxide, by phosphorylation, by esterification, by alkaline hydrolysis, by isothiocyanation, by halogenation, by nitration by carboxylation using mixed anhydrides, cyclic, aliphatic, functionalized, generated in situ or previously.
    [10" id="c-fr-0010]
    10. Use as catalyst, of a material of vegetable origin obtained according to any one of claims 1 to 9, rich in phenolic acids and having fixed at least one metal.
    [11" id="c-fr-0011]
    11. Use as a catalyst and in particular in the homogeneous phase, optionally after acid treatment, of the ash obtained by heat treatment of a material of plant origin obtained according to any one of claims 1 to 9, in the form of an insoluble powder in water, rich in phenolic acids, and having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel ( Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh ), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce), the metal catalyst originating exclusively from material of plant origin without addition of metal originating from Other origin than said material of vegetable origin, for the implementation of organic synthesis reactions involving said catalyst.
    [12" id="c-fr-0012]
    12. Use according to claim 10 or 11 characterized in that said material of plant origin in the form of a powder insoluble in water rich in phenolic acids is preferably chosen from the powder of plant roots, especially hyacinth water (Eicchornia crassipes) or water lettuce (Pistia stratiotes) ', coffee grounds, green and black tea leaves, grape must; lignin including crude lignin and insoluble in water; materials rich in lignin such as cereal straw such as wheat or hemp straw; fiber plants; the woods of deciduous trees such as birch, chestnut, eucalyptus; sawdust including sawdust from poplar, agave, pine or sorghum; cones like pine cones.
    [13" id="c-fr-0013]
    13. Use according to one of claims 10 to 12, characterized in that said material of plant origin rich in phenolic acids is powder of roots of water hyacinths or water lettuce, preferably hyacinth d and in that, preferably:
    the powder from the ends of the roots is used the roots have no aerial parts and / or the material has been dehydrated before use.
    [14" id="c-fr-0014]
    14. Use according to any one of claims 10 to 13 characterized in that the phenolic acids contained in said material of plant origin have been functionalized before fixing at least one metal and in that the functionalization of said phenolic acids is carried out preferably by a Mannich-type reaction such as the Betti reaction, by a diazo coupling reaction, by a transfunctionalization reaction such as the transition from an ester to an amide, the use of amino residues such as dipicolylamine to introduce nitrogenous bonds, by using amino residues for the introduction of a sulfonic group by addition to propane sulfone, by the direct use of taurine, by oxidation of said amino residues such as the oxidation of the pyridine ring to pyridine oxide, by phosphorylation, by esterification, by alkaline hydrolysis or by carboxylation.
    [15" id="c-fr-0015]
    15. Use according to claim 14 characterized in that the phenolic acids contained in said material of plant origin have been functionalized before fixing at least one metal and in that the functionalization of said phenolic acids is preferably carried out by introduction of a functional group chosen from:
    - the aliphatic, cyclic, heterocyclic or aromatic amino, aminoalcohol or di-polyamino groups introduced by a Mannich or related reaction such as the Betti reaction or by a transfunctionalization reaction
    - oxime groups
    - hydroxamic groups
    - the sulfonic groups by a Mannich or related reaction preferably using taurine or by coupling of the diazo compounds or by reaction of sodium sulfite,
    - heterocyclic groups introduced by a Mannich reaction or by nucleophilic substitution or by addition-elimination
    - amide, urea or thiourea groups
    - the carboxylic functions introduced using an acid anhydride or a diacid or derivative of diacid or triacid, derivative of triacid which can be polyfunctional, including nitrogen or sulfur
    - the phosphorus radicals introduced by reaction of a phosphorylation reagent having a phosphoric anhydride group such as P 2 O 5 or polyphosphoric acid functionalized or not or by grafting of P (III) derivatives, by esterification of hydroxy groups or by a phosphate donor such as acetylphosphate, creatine
    - Thiols introduced by a Mannich or related reaction such as the Betti reaction.
    [16" id="c-fr-0016]
    16. Use according to any one of claims 10 to 14 characterized in that the medium in which said material of plant origin in the form of a powder insoluble in water, rich in phenolic acids, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium ( Eu), ytterbium (Yb), cerium (Ce) is either a reaction medium in which a chemical reaction using a metal catalyst has been carried out or an effluent from a reaction medium in which a chemical reaction using u n metal catalyst was carried out, either an effluent of extractive or industrial origin comprising metallic elements.
    [17" id="c-fr-0017]
    17. Use according to claim 16 characterized in that the medium in which said material of vegetable origin, in the form of a powder insoluble in water rich in phenolic acids has fixed at least one metal is either a reaction medium in in which a chemical reaction using a metal catalyst has been carried out, either an effluent from a reaction medium in which a chemical reaction using a metal catalyst has been carried out and in that the fixed metal is chosen in particular from platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru) and in particular palladium (Pd).
    [18" id="c-fr-0018]
    18. Use according to claim 16 characterized in that the effluent is an effluent of extractive or industrial origin comprising metallic elements and in particular an effluent from a quarry and in that the fixed metal is chosen in particular from iron (Fe), manganese (Mn).
    [19" id="c-fr-0019]
    19. Use according to any one of claims 10 to 18 characterized in that the organic synthesis reactions involving said catalyst are chosen from
    - redox reactions such as oxidation, in particular alcohol oxidation, oxidative cleavages, epoxidation, reduction reactions
    - Lewis acid catalysis reactions,
    - reactions of crossed couplings and homocouplings such as reactions of formation of carbon-carbon bonds such as the reaction of Suzuki, the reaction of Heck, the reaction of Sonogashira, the formation of nitrogen-carbon bonds, oxygen-carbon,
    - polymer constructions such as polycondensations,
    - reactions involving Lewis acid catalysis preferably chosen from aromatic electrophilic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, halogenations, reactions of aldolization or crotonization or related reactions such as the condensation reactions of an aldehyde on a di-activated compound of Knoevenagel type, the Perkin reaction, the Tollens reaction, the Thorpe reaction, the Claisen reaction, or the Mukaiyama,
    - multistage reactions including an oxidation or reduction reaction followed by a Lewis acid catalysis
    - isomerization reactions
    - insertion reactions.
    [20" id="c-fr-0020]
    20. Use according to any one of claims 10 to 19 as a catalyst, of a composition containing a metallic catalyst originating, optionally after acid treatment, from the ash obtained by heat treatment of said material of plant origin, in the form of a powder insoluble in water, rich in phenolic acids, having fixed at least one metal in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium ( Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) characterized in that the organic synthesis reactions involving said catalysis ur are chosen from:
    - oxidation reactions
    - reduction reactions
    - cross coupling and homocoupling reactions such as carbon-carbon bond formation reactions such as the Suzuki reaction, the Heck reaction, the Sonogashira reaction, polymerizations, polycondensations
    - reactions involving Lewis acid catalysis preferably chosen from electrophilic aromatic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, transfunctionalization reactions, esterifications , carboxylations, halogenations, aldolization or crotonization reactions or related reactions, preferably Rnoevenagel reactions, Perkin reactions, Claisen reactions, Tollens reactions or Thorpe-Ziegler reactions.
    - multistage reactions including an oxidation or reduction reaction followed by a Lewis acid catalysis
    - isomerization reactions
    [21" id="c-fr-0021]
    21. Use according to one of claims 10 to 19 characterized in that said material of vegetable origin in the form of a powder insoluble in water, rich in phenolic acids having fixed a metal fixed in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru ), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg ), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb) , cerium (Ce) is used in organic synthesis reactions of functional transformations by catalysis chosen from oxidation reactions such as Wacker-Tsuji oxidation, alcohol oxidation, oxidative coupling of compounds aromatic es, reduction such as reduction of olefins and nitro and nitrile compounds or hydrosilylation of olefins and alkynes, catalytic hydrogenation, cross coupling and homocouplings such as carbon bond formation reactions - carbon such as the Suzuki reaction, the Heck reaction, the Sonogashira reaction the nucleophilic addition reactions of an enamine on pi-allylic complexes, Buchwald-Hartwig type reactions, carbonylation reactions and ene-reactions , regioselective reactions between an alkene and an aromatic derivative, cyclopropanation of alkenes, cycloadditions, carbocylization in cascade of polyunsaturated compounds, allyl isomerization, cycloaddition, ene-reactions, cycloisomerizations, hydroboration, polymerization reactions, polycondensations, syntheses of unsaturated and conjugated polymers.
    [22" id="c-fr-0022]
    22. Use according to one of claims 10 to 19 characterized in that said material of vegetable origin in the form of a powder insoluble in water rich in phenolic acids having fixed a metal fixed in ionic form chosen in particular from scandium ( Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru) , palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg) , arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce) is used in organic synthesis reactions of functional transformations by catalysis chosen from the following reactions: oxidation reactions, reduction reactions, cross-coupling and homocoupling reactions, l es reactions involving Lewis acid catalysis preferably chosen from electrophilic aromatic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, halogenations, aldolization reactions or crotonization or related reactions, such as the condensation reactions of an aldehyde on a di-activated compound of the Knoevenagel type, the Perkin reaction, the Tollens reaction, the Thorpe reaction, the Claisen reaction, or the Mukaiyama, oxidation or reduction combination reactions by Lewis acid catalysis, brominations, protections such as chemoselective tritylations of alcohols and amines, acylations, in particular acetylations of alcohols, phenols, thiols and amines, silylations of alcohols, oximes, enolates, phenols, amines and anilines, the form ation of imines or amines, deprotection of functions, in particular detritylation, concerted rearrangements such as ene-reactions or cycloadditions, pinacolic or Beckmann transposition, the Claisen-Schmidt reaction the Mukaiyama reaction or the reactions Knoevenagel type, dehydration or transfunctionalization reactions such as transamination or transtritylation reactions, reactions for preparing polyheterocyclic structures such as porphyrinogens or dithienylpyrroles, multicomponent reactions such as triazole synthesis reactions, reactions of Hantzsch, syntheses of optionally substituted piperidines, biomimetic reactions and hydride transfers.
    [23" id="c-fr-0023]
    23. Use according to one of claims 10 to 19 characterized in that said material of vegetable origin in the form of a powder insoluble in water rich in phenolic acids having fixed Manganese (Mn) and optionally a metal or several metals in ionic form chosen in particular from scandium (Sc), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead ( Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (b), rhodium (Rh), platinum (Pt), lithium (Li ), osmium (Os), mercury (Hg), arsenic (As), antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series in particular europium (Eu), ytterbium (Yb), cerium (Ce) is used in organic synthesis reactions of functional transformations by Lewis acid catalysis chosen oxidation reactions, reduction reactions, reactions cross couplings and homocouplings, aromatic electrophilic substitution reactions (SEAr), pericyclic reactions, multicomponent reactions, cascade reactions, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as the condensation reactions of an aldehyde on a di-activated compound of the Knoevenagel type, the Perkin reaction, the Tollens reaction, the Thorpe reaction, the Claisen reaction, or the Mukaiyama reaction, the combination reactions oxidation or reduction by Lewis acid catalysis, brominations, protections such as chemoselective tritylations of alcohols and amines, acylations, in particular acetylations of alcohols, phenols, thiols and amines, silylations alcohols, oximes, enolates, phenols, amines and anilines, the formation of imines or amines, deprotection of functions in particular detritylation, concerted rearrangements such as ene-reactions or cycloadditions, pinacolic or Beckmann transposition, the Claisen-Schmidt reaction the Mukaiyama reaction or Knoevenagel type reactions, dehydration or transfunctionalization reactions such as transamination or transtritylation reactions, reactions for the preparation of polyheterocyclic structures such as porphyrinogens or dithienylpyrroles, multicomponent reactions such as triazole synthesis reactions, Hantzsch reactions, optionally substituted piperidine syntheses, biomimetic reactions and hydride transfers.
    [24" id="c-fr-0024]
    24. Use according to one of claims 10 to 19 characterized in that said material of plant origin having fixed nickel (Ni) and optionally at least one metal in ionic form chosen from scandium (Se), manganese (Mn ), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), zinc (Zn), ruthenium (Ru), palladium (Pd), cadmium (Cd), iridium (Ir), rhodium (Rh), platinum (Pt), lithium (Li), osmium (Os), mercury (Hg), arsenic (As) , antimony (Sb), chromium (Cr), aluminum (Al) or a metal from the lanthanide series, in particular europium (Eu), ytterbium (Yb), cerium (Ce), is implemented in the reactions chosen from reduction reactions, cross-coupling and homocoupling reactions, reactions involving Lewis acid catalysis preferably chosen from electrophilic aromatic substitution reactions (SEAr), reactions pericyclic, multicomponent reactions, cascade reactions, addition reactions, halogenations, aldolization or crotonization reactions or related reactions such as condensation reactions of an aldehyde on a di-activated compound of Knoevenagel type, Perkin reaction, Tollens reaction, Thorpe reaction, Claisen reaction, or Mukaiyama reaction, halogenation reactions in particular halogenation of primary, secondary and tertiary alcohols (Lucas reaction), reactions aromatic electrophiles in series, substitutions or additions, Friedel-Crafts alkylations, preferably the reaction between toluene and benzyl chloride to obtain 4- and 2-methyldiphenylmethane, acylations of
    Friedel-Crafts preferably the synthesis of methylacetophenone, multicomponent reactions, in particular the Biginelli reaction leading to the synthesis of dihydropyrimidinones or dihydrothiopyrimidinones, preferably 3,4-dihydropyrimidin2 (l //) - one or 3,4 -dihydropyrimidin-2 (177) -thione, and the Hantzsch reaction preferably used to prepare dihydropyridines, the synthesis of 5-ethoxycarbonyl-6-methyl4-isobutyl-3,4-dihydropyrimidin-2 (1H) -one, the reaction between ethyl 3-hydroxybenzaldehyde, ethyl ketopentanoate and thiourea to obtain ethyl 6-methyl-4- (3-hydroxyphenyl) -2thioxo-1,2,3,4-tetrahydro pyrimidine-5-carboxylate (monastrol), cycloaddition reactions, in particular the Diels-Alder reaction such as the reaction of cyclopentadiene with diethyl fumarate or the reaction of 3-buten-2-one with 2,3dimethyl-1,3-butadiene , transesterification reactions, preferably reaction d u methyl and butan-1-ol palmitate, the synthesis of amino acid or oxime complexes, preferably Cu 2+ oxime complexes, catalyzed hydrolysis of organosulfurized functions, in particular thiophosphates such as parathion, catalyst synthesis reactions for hydrogenation reactions after reduction of Ni (II) to Ni (0), reduction reactions such as reduction of 1-phenyl 2-nitroprene to 1-phenyl 2aminopropane, reactions coupling comprising cross-coupling reactions, in particular the Suzuki reaction to preferably synthesize diaryl compounds such as 3-methoxy-4'-methylbiphenyl, the Heck reaction, and the Ullmann reaction (in particular nucleophilic aromatic substitutions such as N and O-arylations), the condensation of diamines on carbonyl derivatives, in particular the synthesis of 1-H-1,5-benzodiazepines preferably from o-phenylenediamine and ac etone, the chemoselective hydrolysis of methyl esters in peptide chemistry, in particular the deprotection of carbonyl groups without cleavage of Fmoc, Fmoc-Gly-OMe and Fmoc-Gly-Phe-Pro-OMe, chemoselective hydrolysis of l 6,7-dideoxy-1,2,2: 3,4-di-O-isopropyldine-7 - [(9fluorenylmethoxycarbonyl) amino] -D-glycero-aD-galacto-octopyranuronic methyl ester to obtain an amino acid derived from galactose, synthesis of 5 'protected oligonucleotides, synthesis of 5'-GpppT 6 and 5'-GpppRNAs, coupling of phosphoroimidazolidate Té on solid support with GDP in particular synthesis of 5'-guanosyl triphosphate hexa- 2'-deoxythymidylate (GpppT 6 ), reductive aminations, preferably catalyzed formation of imines followed by their reduction in situ, synthesis of secondary amines and substituted anilines, chlorination of alkenes such as chlorination dicyclopentadiene, aromatic halogenation reactions without dihalogen, synth se of bromo- and iodoanisole, successive or cascade reactions such as addition, dehydration, cycloaddition, or electrocyclization reactions, synthesis of benzopyranes and cannabinoids or dihydrocannabinoids and in particular the condensation of diamines on derivatives carbonylated, reductive aminations, Aromatic halogenation reactions without dihalogen, the Ullmann reaction successive or cascade reactions such as addition, dehydration, cycloaddition or cyclization reactions, the Suzuki reaction, aromatic electrophilic reactions in series, substitutions or additions, multicomponent reactions, in particular the reaction of
    5 Biginelli.
    [25" id="c-fr-0025]
    25. Process for depolluting industrial effluents from, for example, mines, quarries or the steel industry, said process being characterized by the following steps:
    a treatment of an industrial effluent with a material of plant origin rich in phenolic acids in the form of a powder insoluble in water, and
    -filtration to recover said material of plant origin rich in phenolic acids which have fixed the metal or metals in ionic form present in the industrial effluent.
    1/1 • SA_pallle_de_ble Éduntllon 024 By CNRS Date Tuesday, Jullet 18 ...
    • Café Iaveh2o toi Échantilon 011 By CNRS Date Wednesday, March ...
    YY'î
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    同族专利:
    公开号 | 公开日
    WO2018178371A1|2018-10-04|
    EP3600661A1|2020-02-05|
    WO2018178374A1|2018-10-04|
    EP3600658A1|2020-02-05|
    US20200047165A1|2020-02-13|
    FR3064496A1|2018-10-05|
    US20200039856A1|2020-02-06|
    US11254597B2|2022-02-22|
    CA3058264A1|2018-10-04|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1752822|2017-03-31|
    FR1752822A|FR3064496A1|2017-03-31|2017-03-31|USE OF NATURAL MATERIALS OF VEGETABLE ORIGIN RICH IN PHENOLIC ACIDS FOR THE IMPLEMENTATION OF ORGANIC CHEMICAL REACTION AND RECYCLING OF CATALYSTS|US16/498,912| US11254597B2|2017-03-31|2018-03-30|Method for the production of a material of plant origin that is rich in phenolic acids, comprising at least one metal, for carrying out organic synthesis reactions|
    PCT/EP2018/058362| WO2018178374A1|2017-03-31|2018-03-30|Method for the production of a material of plant origin that is rich in phenolic acids, comprising at least one metal, for carrying out organic synthesis reactions|
    EP18722898.6A| EP3600661A1|2017-03-31|2018-03-30|Method for the production of a material of plant origin that is rich in phenolic acids, comprising at least one metal, for carrying out organic synthesis reactions|
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