EP3021963A1 - Verwendung bestimmter platinoidspeichernder pflanzen zur verwendung in organisch-chemischen reaktionen - Google Patents

Verwendung bestimmter platinoidspeichernder pflanzen zur verwendung in organisch-chemischen reaktionen

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Publication number
EP3021963A1
EP3021963A1 EP14750569.7A EP14750569A EP3021963A1 EP 3021963 A1 EP3021963 A1 EP 3021963A1 EP 14750569 A EP14750569 A EP 14750569A EP 3021963 A1 EP3021963 A1 EP 3021963A1
Authority
EP
European Patent Office
Prior art keywords
acid
chosen
rhodium
palladium
plant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14750569.7A
Other languages
English (en)
French (fr)
Inventor
Claude Grison
Vincent ESCANDE
Clémence BES
Brice-Loïc RENARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite de Montpellier
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Montpellier
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Montpellier filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3021963A1 publication Critical patent/EP3021963A1/de
Withdrawn legal-status Critical Current

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    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to the use of platinum group metal accumulator plants (platinoids) for the implementation of chemical reactions.
  • CNRS is studying the phytostabilisation technique, which involves planting soil contaminated by plants capable of growing in the presence of heavy metals ( speak of tolerance) (Frérot et al., Specifies interactions between local metallicolous plants to improve phytostabilazation of mines, Plant and Soil, 282, 53-65, 2006). Some of these plant species used have the particularity of accumulating metals in large quantities in their vacuoles (we speak of hyperaccumulating plants). It is then phytoextraction.
  • Thlaspi caenilescens (synonym Noccaea caenilescens) belonging to the family Brassicaceae, has remarkable properties of tolerance and hyperaccumulation of zinc, cadmium, nickel. It concentrates them at the level of the aerial parts (leaves and stems). This plant is able to store 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 low concentrations of these two metals.
  • Zinc chloride is one of the most used and is indispensable in many industrial and laboratory reactions. It is also frequently used in heterocyclic organic chemistry to catalyze many electrophilic aromatic substitutions. It is also a catalyst of choice for carrying out the hydrogenations of primary alcohols with the Lucas reagent, the acetalization reactions, aldolization or Diels-Alder type cycloaddition reactions.
  • the catalysts are also very useful in analytical electrochemistry, electrometallurgy and liquid-solid extraction where the fields of application are numerous and directly involved in the different fields of economic life (batteries, batteries and accumulators, spectroscopic apparatus detectors, metallurgy, welding ...)
  • Thlaspi caendescens now called Noccaea caendescens and Anthyllis vulneraria
  • WO 201 1/064487 describes the use of many other metallophyte hyperaccumulative heavy metal plants for the preparation of catalysts for use in organic chemistry.
  • the invention described in WO 201 1/064487 relates to the use of a calcined plant or part of a calcined plant having accumulated at least one metal in M (II) form chosen especially from zinc ( Zn), nickel (Ni) or copper (Cu) as defined above, wherein said plant is chosen in particular from the family Brassicaceae, including species of the genus Thlaspi (synonym Noccaea) in particular T. goesingense, T. tatrense, T. rotundifolhim, T. praecox, species of the genus Arabidopsis, in particular Arabidopsis hallerii, and of the genus Alyssum, in particular A. bertolonii, A.
  • Thlaspi species of the genus Thlaspi (synonym Noccaea) in particular T. goesingense, T. tatrense, T. rotundifolhim, T. praecox, species of the genus Arab
  • the plants of the genus Sedum are succulent plants that belong to the crassulaceae family, composed of more than 400 species. They have natural abilities to grow on poor, dry, open soil and difficult conditions. Their foliar system is fleshy and their crops are well-off.
  • Sedum phimbizincicola and Sedum jinianum have a remarkable ability to extract zinc from polluted soils in southern and eastern China. They have a real potential in phytoextraction and are called "plumbizincicolafor".
  • Examples of plant genera with hyperaccumulator species of manganese are: Alyxia, Azolla, Beauprea, Bea preopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Genia, Garciania, Gleichenia, Gossia, Grevillea, Macadamia, Maytemis, Pimis, Spermacone, Stenocarp, Virotia.
  • the bio-sourced catalysts make it possible to develop heterogeneous catalysts which are very interesting because they can be recovered by simple filtration and rinsing; they are therefore recyclable.
  • the present application therefore has for first object, the use after heat treatment of a plant or part of a plant belonging to one of the genera selected from the green arum (Peltandra virginica), the cucumber (Cucumis sativus) , watercress (Lepidhim sativ tn), Canada water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays) , white mustard (Sinapis alba), brown mustard (Brassica j ncea), barley (Hordeum vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Raphan s sativus), common ryegrass (Loli m perenne), Italian ryegrass (Lolium midtiflorum), whorled fox
  • the invention also relates to the use as a catalyst of a composition containing a metal catalyst derived after acid treatment of the ash obtained after thermal treatment of a plant or part of a plant belonging to one of the genera chosen from green arum (Peltandra virginica), cucumber (Cucumis sativus), watercress (Lepidium sativum), Canada water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes) , alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordenm vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Raphamis sativiis), common ryegrass (Lolhim perenne), ryegrass (Lo
  • the subject of the invention is also the use as described above, characterized in that the heat treatment of a plant or part of a plant is carried out in air.
  • the subject of the invention is also the use as described above, characterized in that the heat treatment of a plant or part of a plant is carried out under an inert gas atmosphere, preferably argon.
  • the present application also relates to the use of a composition prepared by heat treatment of a plant or part of a plant belonging to one of the genera chosen from the green arum (Peltandra virginica), the cucumber ( Cucumis sativus), watercress (Lepidhim sativum), Canada water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Raphamis sativus), common ryegrass (Lolium perenne), Italian ryegrass (Lolium multiflorum), whorled foxtail (Setaria verticill
  • the present application also relates to the use of a composition prepared by heat treatment with air of a plant or part of a plant belonging to one of the genera selected from the green arum (Peltandra virginica) , cucumber (Cucumis sativus), watercress (Lepidium sativum), Canada water lily (Elodea ccmadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), 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 (Lolhim perenne), Italian ryegrass (Lolhtm multifloriim), whorled
  • the present application also relates to the use as described above after heat treatment followed by acid treatment of a plant or part of a plant selected from the genus selected from the green arum (Peltandra virginica). ), cucumber (Cucumis sativus), watercress (Lepidium sativum), Canada water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa) , maize (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish ( Raphanus sativus), common ryegrass (Lolhtm perenne), Italian ryegrass (Lolium multiflorum), whorled fox
  • the present application also relates to the use as described above after heat treatment followed by acid treatment of a plant or part of a plant selected from the genus selected from the green arum (Peltandra virginicd) , cucumber (C citmis sativus), watercress (Lepidhim sativum), Canada water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativd) , maize (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vi station), nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Rophomis sativus), common ryegrass (Lo ⁇ him perenne), Italian ryegrass (Loliiun ltiflor m
  • the subject of the present invention is also a process for the preparation of a composition comprising a metal or polymetallic agent comprising at least one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium and rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh) characterized in that it comprises the following steps: a) Dehydration, preferably at room temperature or in an oven at a temperature of the order of 70 ° C of the biomass comprising the leaves, stems and / or roots of a plant or plant extract belonging to one of the genera selected from the green arum ⁇ Peltandra virginica), the cucumber (Cucumis sativus), watercress (Lepidhim sativ m), Canada seaweed (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago
  • step b) milling the dry biomass of a plant or a plant extract obtained in stage a) optionally in the presence of a salt or a mixture of salts, preferably sodium chloride and potassium disulfate, c) Heat treatment with air or argon of the biomass obtained in step a) or the ground mixture obtained in step b) in a furnace preferably in one or more steps preferably in a step at 500-600 ° for several hours, preferably for about 2 hours or in two stages the first to a temperature below 500 ° C, preferably of the order of 350 ° and at a second stage at a temperature of the order of 550 ° each of these steps being carried out for about 3 hours
  • stage c) treatment of the ash obtained in stage c) with a salt or a mixture of several salts, preferably a mixture of sodium chloride and potassium disulphate so as to obtain a melted mixture after heating
  • an acid solution said acid being preferably chosen from hydrochloric acid, preferably at a concentration chosen between 1M and 12M, or nitric acid, sulfuric acid, trifluoromethanesulfonic acid, nitric acid, formic acid, oxalic acid, perchloric acid, phosphoric acid, trifluoroacetic acid or para-acid
  • toluene sulphonic acids are preferably used at a high concentration, preferably from 10 to 30%, followed, if desired, by filtration preferably on celite and dehydration of the solution or suspension preferably obtained under reduced pressure. to obtain a dry residue which can be dried at 120 ° C, and, if desired,
  • stage d) of the process the optional obtaining of a molten mixture between the ashes obtained in stage c) and the acid salts is preferably carried out with plants or parts of Rhodium accumulating plants.
  • the subject of the present invention is therefore a process characterized in that when steps a) to c) of the process are carried out with rhodium-accumulating plants, the ashes obtained in stage c) are treated with a salt or a mixture of several salts. preferably a mixture of sodium chloride and potassium disulfate so as to obtain a molten mixture.
  • the catalysts derived from the accumulating platinum-forming biomasses are prepared as follows: Specific preparation of palladium or platinum catalysts:
  • the leaves, stems or preferably the collected roots are dehydrated, either at room temperature or in an oven (70 ° C).
  • the dry mass obtained is subjected to a heat treatment at 550 ° C. for 2 hours in air (Eco-Pd cat i) or under argon (Eco-Pd ca t2) in order to destroy the organic matter.
  • the catalysts, Eco-Pd catl and Eco-Pd cat2> mixtures of polymetallic species and organic material, are used directly or stored for the following catalyst preparation operations.
  • Acid treatment of Eco-Pd cat i and Eco-Pd cat 2 from biomass catalytic type 2: Eco-Pd cat 3 and Eco-Pd cat4
  • the Eco-Pd cat and Eco-Pd cat2 catalysts obtained after thermal treatment of the biomass are introduced into an Erlenmeyer flask equipped with a magnetic bar, then an acid solution, which, when hydrochloric acid is used, can have a concentration. between 1 and 12 M is introduced gradually, with stirring.
  • Other acids such as nitric or sulfuric acid can be used in high concentrations, preferably from 10 to 30%.
  • Pd ca t4 obtained following the previous treatment, in particular to form a catalyst in the form of acetate, more soluble in organic solvents.
  • 100 mg of Eco-Pd cat 3 are introduced into a flask fitted with a magnetic stirring bar, then 10 ml of 95% acetic acid and 60 ⁇ l of nitric acid (65%) are added. The resulting solution is stirred at reflux for 3 hours. This is then concentrated under reduced pressure until an orange solid is obtained. This solid is taken up with a solvent such as acetone or ethyl acetate. Evaporation of this organic phase leads to the catalyst being obtained in acetate form.
  • Catalyst supported on mineral support catalyst type 4 Different mineral supports can be used to support the catalyst and thus perform a supported catalysis. Typically, montmorillonite K10, silica, alumina or hydrotalcite have been used as support. 1 g of mineral support is introduced into a balloon fitted with a magnetic bar, then 50 mg of type 2 or 3 catalyst are added. 10 ml of water are added and the resulting suspension is then stirred at ambient temperature for 5 hours. This is then filtered, the solid is washed with 10 ml of distilled water, and the latter is collected for drying in an oven (120 ° C.). during one night. Once its mass is stabilized, the resulting catalyst is stored in the desiccator.
  • montmorillonite K10, silica, alumina or hydrotalcite have been used as support. 1 g of mineral support is introduced into a balloon fitted with a magnetic bar, then 50 mg of type 2 or 3 catalyst are added. 10 ml of water are added and the resulting suspension is then stirred at
  • the catalyst may also be supported on organic solids, in particular of natural origin, such as chitosan derivatives.
  • organic solids in particular of natural origin, such as chitosan derivatives. This involves the preparation of an organic support from chitosan according to the following procedure: in a flask equipped with a magnetic ban-water are introduced: 15 ml of methanol, 1 g of chitosan, 1.6 g (15 mmol ) 2-pyridinecarboxaldehyde, 1.5 mL (26 mmol) concentrated acetic acid. The whole is refluxed, with stirring, for 10 h, under a stream of dinitrogen.
  • Catalyst treated with a reducing organic acid, formic acid or oxalic acid catalyst type 6: Eco-Pd ca t7 and Eco-Pd ca t8
  • the Pd (II) of the polymetallic catalyst can be reduced to Pd (0) by dihydrogen, hydrazine, sodium borohydride, formaldehyde, but the search for green conditions rather suggests the use of formic acid or one of these salts, or oxalic acid.
  • the oxides obtained after thermal treatment of the biomass are ground in a mortar with a mixture of sodium chloride and potassium disulphate.
  • the mixture is placed in a Pyrex crystallizer or porcelain crucible and then heated in an oven at 500-600 ° C for 2 hours.
  • the finely ground reddish solid is introduced into a concentrated aqueous hydrochloric acid solution, stirred for 1 hour under reflux.
  • the resulting solution is concentrated by evaporation under reduced pressure until a catalytic solid is obtained. This is recovered and its drying is completed in an oven (120 ° C) until stabilization of the mass of the solid.
  • This catalyst is then stored in a desiccator.
  • a high purity catalyst can be prepared by precipitation of the RhCl (PPh 3 ) 3 complex.
  • An example of such a preparation is given below in the experimental part.
  • a high purity catalyst can be obtained by purification on ion exchange resins.
  • the ion exchange technique is widely used for the recycling and separation of Rhodium from other platinoids, transition metals and alkali metals.
  • the rhodium complexes can be purified for example on cation exchange resins such as Wafatit KPS-200 or Vionit CS-3.
  • the present application also relates to a method characterized in that the plants belonging to one of the genera selected from the green arum ⁇ Peltandra virginica), the cucumber (Cucumis sativus), the cress (Lepidhim sativum), the elodea (Elodea canadensis), spinach (Spinacia oleraced), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vulgare), stinging nettle (Urtica dioica), phacelia (Phacelia tanacetifolid), radish (Raphanus sativus), common ryegrass (Loiumium perenne), ryegrass (Lolium multiflorum), foxtail (Setaria verticillata) and tobacco (Nico
  • the preferred procedure is to use effluents contaminated with PGE, to preferably subject these effluents to an acidification treatment in order to lower the pH in a range between pH 3 and pH 6 to increase the solubility of PGEs and the availability of PGE for the plants and then cultivate potentially hyperaccumulative plants in contact with its effluents.
  • the subject of the invention is therefore a process characterized in that the effluents contaminated with one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium and rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh) are treated with an acid chosen preferably from hydrochloric acid, nitric acid, sulfuric acid, trifluoromethanesulphonic acid, nitric acid, perchloric acid, phosphoric acid or an organic acid such as acetic acid, citric acid, malic acid, lactic acid so as to obtain a solution whose pH is preferably between 3 and 6 before being brought into contact with the plants accumulators of the platinoids.
  • platinum (Pt), palladium (Pd) or rhodium (Rh) are treated with an acid chosen preferably from hydrochloric acid, nitric acid, sulfuric acid, trifluoromethanesulphonic acid, ni
  • the subject of the invention is also a process characterized in that the effluents contaminated with one of the platinoids chosen from platinum, palladium, osmium, iridium, ruthenium and rhodium, preferably platinum (Pt), palladium (Pd) or rhodium (Rh) are treated with an acid preferably selected from hydrochloric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, nitric acid, perchloric acid, or phosphoric acid, preferably nitric acid used alone, so as to obtain a solution whose pH is preferably between 2 and 6 before being brought into contact with the accumulator plants of the platinoids.
  • platinum palladium
  • osmium iridium
  • an acid preferably selected from hydrochloric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, nitric acid, perch
  • the subject of the invention is therefore a process characterized in that the cultures of plants belonging to one of the genera chosen from among the green arum (Peltandra virginica), the cucumber (Cucumis sativus) and the cress (Lepidi m sativum).
  • the platinoid storage plants are cultivated as follows: 1) Cultivation on uncontaminated sand:
  • the species are germinated in pots containing sterile sand and placed in large tanks containing the culture solution, starting with water and fertilizer. Then after 2 weeks of growth, the culture solution is replaced by a new solution consisting of previously thermally treated effluents then taken up by H 0 3 (and optionally neutralization with ammonia) and fertilizer. After 4 weeks of exposure the roots and aerial parts of the plants are harvested, washed, dried and weighed. The samples are then burned in a muffle furnace at 350 ° C for 3 hours and then at 550 ° C for 3 hours. Then the ashes are used for the preparation of the catalysts. This method is optimal for plants that can not be grown in hydroponics and less tolerant of excess PGE. High concentrations in the roots are reached.
  • the species are germinated in tubes of coconut "fleximix root it organic Starter Cubes". This substrate consists of fibers, peat and coconut bark.
  • the seeds of each species are then grouped on seedlings watered with water, on a daily basis to avoid drying out. For 15 days, the seedlings are arranged under neon lights under a light output of 1 1000 lumens.
  • the monitoring of the germination rate of the 260 seeds of 3 species, Brassica juncea, Lolhim multiflorum and Sinapsis alba shows particularly interesting values for Brassica juncea, and especially Lolhim multiflorum. The optimal value is around 12 to 13 days.
  • the germination rates are as follows:
  • Brassica juncea 78.5%; Lolium multiflorum: 84.6%; Sinapis alba: 48%
  • a growth protocol through one of the clay balls placed in baskets, deposited in turn on clay balls placed at the bottom of the vat of culture makes it possible to optimize the root growth.
  • the clay balls make it possible to move the roots away from the nutrient solution and to promote the growth of the primary root. Fertilizers introduced into the nutrient solution must be introduced in low concentrations so as not to burn the young roots.
  • the plants are then transplanted and placed under mercury lamps that provide a light output of 37,000 lumens.
  • This lighting system promotes the development of the plant placed in hydroponics, but also the evapotranspiration of plant species, engine of root absorption.
  • An evolution of the average length of the longest root over time shows a rapid and continuous growth of the initial primary root for Lolium.
  • the inter-specific comparison of the size of the largest root at 40 days gives the following results:
  • Brassica juncea 40 cm; Lolium multiflorum: 8 cm; Sinapis alba: 8 cm
  • the effluent is an aqueous solution whose metal species are derived from organic reactions, such as coupling reactions such as the Suzuki reaction.
  • the salts were previously heat-treated and then with HNO 3 (and optionally neutralization with ammonia).
  • HNO 3 and optionally neutralization with ammonia.
  • the solution to be reprocessed is rich in palladium nitrate or a derivative salt such as ammonium palladium nitrate.
  • An ideal concentration is close to 40 mg / L and the pH should be kept at 3, in order to avoid the precipitation of salts.
  • the pH must be adjusted to the nature of each salt.
  • the samples are then burned in a muffle furnace at 350 ° C for 3 hours and then at 550 ° C for 3 hours.
  • the heat treatment is carried out either in air or under argon.
  • the ashes are used for the preparation of the catalysts. This method is optimal because it allows to quickly have a large biomass and allows a better accumulation of roots, it is ideal for aquatic plants and / or tolerant to excess PGE.
  • the subject of the invention is therefore a process for cultivating plants belonging to one of the genera chosen from among the green arum ⁇ Peltandra virginica), the cucumber (Cucumis sativus), the watercress (Lepidium sativum), the Pélodée du Canada ( Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea ays), 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)
  • the subject of the invention is therefore a process for cultivating plants belonging to one of the genera chosen from among the green arum (Peltandra virginica), the cucumber (Cucumis sativus), the cress (Lepidium sativum), the elodea of the Canada (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard ( Brassica j ncea), barley (Hordeum v lgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifolid), radish (Raph nus sativus), common ryegrass (Lolhim perenne), Italian grass (Lolhim midtiflorum), whorled foxtail (Setaria verticillat
  • the subject of the invention is in particular a method for cultivating plants belonging to one of the genera chosen from among the green arum (Peltandra virginica), the cucumber (Cucumis sativus), the cress (Lepidium sativum), the elodea of the Canada (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard ( Brassica juncea), barley (Hordeum vulgare), stinging nettle (Urtica dioica), phacelia (Phacelia tanacetifolia), radish (Raphanus sativus), common ryegrass (Lolhim perenne), ryegrass Italy (Lolhim multiflorum), foxtail (Setaria verticillata) and tobacco (
  • the present invention also relates to a method for treating effluents contaminated with PGE in order to remedy the contaminated media while providing an alternative source of PGE useful for catalysis purposes for the green chemistry industry.
  • the subject of the present invention is also a process as described above, characterized in that the aqueous phase of the reaction mixture obtained after using, as catalyst, compositions containing a metal catalyst derived after acid treatment of the ashes obtained after thermal treatment of a plant. or a plant part as described above is recycled by rhizofiltration using said plants.
  • the subject of the invention is therefore a method for decontaminating the effluents contaminated by at least one platinoid chosen from platinum, palladium, osmium, iridium, ruthenium and rhodium, characterized in that plants capable of accumulating at least one of the platinoids belonging to one of the genera selected from the green arum (Peltandra virginicd), the cucumber (Cucumis sativus), the watercress (Lepidium sativum), the Canadian water lily (Elodea canadensis), spinach (Spinacia oleracea), water hyacinth (Eicchornia crassipes), alfalfa (Medicago sativa), corn (Zea mays), white mustard (Sinapis alba), brown mustard (Brassica juncea), barley (Hordeum vulgare), nettle (Urtica dioica), phacelia (Phacelia tanacetifoli
  • the overall procedure is the same as that indicated above, it consists in recovering effluents contaminated with PGE, treating these effluents to increase the solubility of the PGEs and then cultivating potentially hyperaccumulating plants in contact with these effluents.
  • Two methods are possible: 1) using effluents to water plants grown in an uncontaminated medium (eg sand) or 2) growing plants hydroponically directly in the contaminated medium (effluents). Of many species are able to collect the PGEs and some are able to concentrate them in their roots at a very high concentration.
  • the subject of the present invention is also the use in which the composition containing at least one metallic or preferably polymetallic catalyst as described above is used in the implementation of the organic synthesis reactions of functional transformations by catalysis chosen from the carbon-carbon bond formation reactions selected from Suzuki reaction, Heck reaction, Sonogashira reaction, aryl coupling reactions selected from Kumada reaction, Negishi and Fukuyama reaction, Hiyama reaction, and the reaction of Stille; the nucleophilic addition reactions of an enamine on the pi-allylic complexes, the Buchwald-Hartwig type reactions, the carbonylation reactions and the ene-reactions, the oxidation of Wacker-Tsuji, the oxidation of alcohols, the oxidative coupling of aromatic compounds, regioselective reactions between an alkene and an aromatic derivative, cyclopropanation of alkenes, reduction of olefins and nitro compounds, hydrosilylation of olefins and alkynes, cycloadditions, cascade
  • the subject of the present invention is also the use of a composition containing at least one metallic or preferably polymetallic catalyst as described above for carrying out the organic synthesis reactions of functional transformations by catalysis chosen from the reactions of formation of carbon-carbon bonds such as the Suzuki reaction, the Heck reaction, the Sonogashira reaction, nucleophilic addition reactions of an enamine on pi-allylic complexes, Buchwald-Hartwig type reactions, carbonylation reactions and ene-reactions, Wacker-Tsuji oxidation, alcohol oxidation, reduction of olefins and nitro and nitrile compounds, hydrosilylation of olefins and alkynes, allylic isomerization.
  • catalysis chosen from the reactions of formation of carbon-carbon bonds such as the Suzuki reaction, the Heck reaction, the Sonogashira reaction, nucleophilic addition reactions of an enamine on pi-allylic complexes, Buchwald-Hartwig type reactions, carbonylation reactions and ene-reactions, Wacker
  • the present invention more particularly relates to the use as described above wherein the reaction is selected from the Suzuki reaction, the reaction of Heck, the reaction of Sonogashira, and the reduction of olefins and nitro compounds and nitriles.
  • the present invention more particularly relates to the use as described above in which the reaction is selected from the formation of carbon-carbon bonds via the Heck reaction, the Suzuki reaction, the green reductions.
  • the present invention more particularly relates to the use as described above characterized in that the metal catalyst or preferably polymetallic Palladium preferably contained in the composition as described in one of these claims for the implementation organic reaction reactions of catalytic functional transformations selected from among the Suzuki reaction, the Heck reaction, the Sonogashira reaction, and the reduction of olefins and nitro compounds, is used at very low doses, for example example of the order of at least 0.001 mol% to 0.15 mol%, preferably of the order of at least 0.0025 mol% of Pd.
  • the present invention more particularly relates to the use as described above characterized in that, in the composition containing at least one mono or polymetallic agent used in the implementation of organic synthesis reactions of functional transformations by catalysis, the metal concentration is between 600 and 120,000 mg.kg- 1 for platinum, between 5,000 and 180,000 mg.kg- 1 for palladium and between 30 and 22,000 mg-kg- 1 for rhodium.
  • compositions containing at least one metallic or preferably polymetallic catalyst as described above in the implementation of the organic synthesis reactions of functional transformations by catalysis is preferably carried out under the following conditions: Bio-sourced chemistry of palladium
  • biobased catalysts that are the subject of the present application is their ability to catalyze the formation of carbon-carbon bonds with very small amounts of catalysts.
  • This aspect is fundamental, given the particularly high cost of EMPs. This aspect is illustrated in detail with the reactions of carbopalladations of the Heck type and of cutting such as the reaction of
  • Ar mono or polycyclic aromatic radical, carbocyclic or heterocyclic, preferably phenyl or naphthyl.
  • Aryl can be mono or disubstituted.
  • the reaction can also be performed by replacing the Ar group with a vinyl group
  • R 1 aromatic group, COOR, CHO, C (O) R, CN, P (O) (OR) 2 in which R represents an alkyl radical having from 1 to 6 carbon atoms.
  • R 1 aromatic group, COOR, CHO, C (O) R, CN, P (O) (OR) 2 in which R represents an alkyl radical having from 1 to 6 carbon atoms.
  • phosphine ligands are not useful.
  • the present process does not require organic ligands, palladium being readily reduced in situ by the species present in the reaction medium as described in (a) Beletskaya, I. P .; Cheprakov, A. V., The Heck Reaction to a Sharpening Stone of Palladium Catalysis. Chemical Reviews 2000, 100 (8), 3009-3066; (b) Ziegler, C. B .; Heck, R.F., Palladium-catalyzed vinylic substitution with highly activated aryl halides. The Journal of Organic Chemistry 1978, 43 (15), 2941-2946. This is a significant advantage given their cost and chemical or thermal instability.
  • the absence of phosphine ligands also reflects the good stability of the biosourced catalytic systems.
  • Ar and Ar ' represent a mono- or polycyclic, carbocyclic or heterocyclic aromatic radical, mono- or disubstituted, preferably a phenyl or a naphthyl.
  • the reaction can also be carried out by replacing the group Ar or Ar 'with a vinyl group
  • the catalysts of type 1, 2, 3 and 4 prove very effective for this reaction, in heterogeneous catalysis. These can be reused after reaction and reactivation by washing and drying. They can also be recycled by plants according to the method described in the rhizofiltration part.
  • the reaction is general, including with non-activated halogenated derivatives, including chlorinated ones.
  • the nature of the thermal treatment of biomass slightly affects the catalytic activity; it is better to use a heat treatment in the air.
  • the acid treatment brings a very important beneficial effect.
  • the comparison of the results with Plos One 2014, 9, issue 1, e87192 (Parker et al) are suggestive.
  • the authors describe examples of Suzki reaction involving 12 mol% palladium. If the Eco-Pd catalysts of type 1, 2, 3 and 4 have a catalytic activity, Eco-Pd cat 3 leads to very good yields from 0.0025% of Pd!
  • the reactivity of the ⁇ -allyl complexes is illustrated by the nucleophilic addition of an enamine to a ⁇ -allylic complex.
  • the Buchwald-Hartwig reaction has been illustrated in a cyanation version, based on the use of copper (I) thiocyanate in place of the conventionally used highly toxic cyanides.
  • the biosourced Pd catalysts can also catalyze these two families of reaction from the same substrate.
  • Wacker-Tsuji allows the production of ketones from alkenes in a process of industrial importance (industrial synthesis of ethanal to from ethene).
  • Biobased Pd catalysts effectively catalyze the reaction and can be readily recycled when supported (particularly for type 3 catalyst).
  • the controlled oxidation of a primary alcohol to aldehyde by dioxygen is quantitative when catalyzed by biobased Pd catalysts.
  • Nucleophiles such as alcohols or amines are capable of adding to a double or triple bond by type 2 or 3 biosourced Pd catalysis, the chemo-selectivity being different depending on the type of catalyst used. This is a good way to access heterocycles.
  • Functionalized cyclopropanes which are present in many molecules of industrial interest, can be obtained from biobased Pd-catalyzed alkenes and diazotized reagents.
  • the catalyst reacts actively on the hydrolysis of sodium borohydrides with hydrochloric acid which liberates hydrogen. This in situ generated hydrogen reduces adsorption double bonds on Pt (0). Triple bonds also react. Lowering the reaction temperature to -25 ° C from the same assembly considerably increases the selectivities of the catalysis.
  • Hydrosilylation of unsaturated compounds is a commonly used reaction in the silicone industry that can be catalyzed by biosourced Pt catalysts.
  • Metathesis and cycloisomerization of enynes are two examples of cycloaddition efficiently catalyzed by biosourced Pt catalysts.
  • the biosourced Pt catalysts make it possible to carry out the carbocyclization in cascade of polyunsaturated compounds.
  • the reaction is conducted with a hydride donor simple to produce (by Hantzsch reaction) and without danger of manipulation.
  • the reaction works as efficiently on electron-enriched alkenes as on non-enriched unsaturated derivatives.
  • the use of an insoluble ligand (chitosan-pyridyl) makes it possible to reuse the catalyst at the end of the reaction by simple filtration:
  • Cycloadditions such as cyclotrimerization [4 + 2 + 2] of enyne with 1,3-butadiene can be facilitated by biobased Rh catalysis.
  • R alkyl, aryl, heteroatom
  • Example 1.2 Aryl coupling reaction with organometallic compounds, example of a typical Suzuki reaction
  • Example 1.3 Chemistry of the ⁇ -allyl complexes The reactivity of the ⁇ -allyl complexes is illustrated by the nucleophilic addition of an enamine to a ⁇ -allylic complex.
  • Example 2.1 Oxidation of Wacker-Tsuji: oxidation of decene
  • type 2 or 4 catalyst 0.1 equivalent Pd
  • CuCl 1 equivalent
  • a mixture DMSO / water 7/1.
  • the whole is fed with oxygen by a balloon stung through a septum surmounting the reaction setup.
  • the whole is stirred vigorously to allow the enrichment of the solution in 0 2 at AT.
  • 1-decene (1 equivalent) is introduced dropwise over 10 minutes.
  • the medium is stirred for 24 h at RT, under a dioxygen atmosphere.
  • GC-MS analyzes indicate a yield of dodecanone of 70%.
  • Vibration bands at 1442 cm -1 and between 1599 and 1624 cm -1 reflect the Lewis acidity of the catalyst.
  • Several types of Lewis acid sites are highlighted. The acidity of Lewis is different from that observed with commercial PdCl 2 : the signals around 1600 cm -1 have a higher frequency than for PdCl 2, which suggests that certain Lewis acid sites are stronger than in PdCl 2 .
  • the signals at 1448 and 1606 cm -1 correspond to the acidity of Lewis, close to PdCl 2 .
  • a signal marked at 1527 cm -1 is weak and therefore difficult to assimilate to the Brönsted acidity
  • the signal at 1636 cm -1 can be due to a stronger Lewis acidity.
  • Eco-Pd cat 4 and Eco-Pd cat3 have a different and complementary acidity. Eco-Pd ca t 4 is clearly distinguishable from commercial PdCl 2 .
  • the analyzes are performed with the Thermo Electron ESCALAB 250.
  • the excitation source is the monochromatic source, line Al Ka (1486.6 eV).
  • the analyzed surface has a diameter of 400 ⁇ .
  • the photoelectron spectra are calibrated as binding energy with respect to the energy of the C-C component of the Cls Carbon at 284.8 eV.
  • the powder is dispersed on a graphite scotch.
  • the quantization step consists of counting the electrons emitted by the various constituents of the material. Without the use of reference samples, all the electrons collected are considered to represent 100% of the constituents of the sample. It is therefore a method of semi-quantification.

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SE540693C2 (sv) 2014-03-20 2018-10-09 Scania Cv Ab Förfarande för att styra en hybriddrivlina, fordon med en sådan hybriddrivlina, datorprogram för att styra en sådan hybriddrivlina, samt en datorprogramprodukt innefattande programkod
SE539028C2 (sv) 2014-03-20 2017-03-21 Scania Cv Ab Förfarande för ivägkörning av ett fordon med en hybriddrivlina, fordon med en sådan hybriddrivlina, datorprogram för attstyra ivägkörning av ett fordon, samt en datorprogramproduk t innefattande programkod
SE539662C2 (sv) 2014-03-20 2017-10-24 Scania Cv Ab Förfarande för att starta en förbränningsmotor i en hybriddrivlina, fordon med en sådan hybriddrivlina, datorprogram föratt starta en förbränningsmotor, samt en datorprogramproduk t innefattande programkod
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US11319232B2 (en) 2017-03-31 2022-05-03 Centre National De La Recherche Scientifique Treatment of quarry liquid effluent
CN116199800A (zh) * 2023-02-08 2023-06-02 中国林业科学研究院林产化学工业研究所 一种具有抗弧菌活性的壳聚糖-柠檬醛-钙盐复合物的制备方法
CN116199800B (zh) * 2023-02-08 2024-02-27 中国林业科学研究院林产化学工业研究所 一种具有抗弧菌活性的壳聚糖-柠檬醛-钙盐复合物的制备方法

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