Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/20—Metals
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
  • G01N31/02—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using precipitation
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
  • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators

Definitions

• the present invention relates to a method suitable for detecting, capturing and / or selective releasing of chemical elements selected from poor metals, alkalis, alkaline earths, actinides and rare earths. These processes use a molecular assembly formed of at least one amine, at least one aldehyde and / or imine and / or C0 2 , or an adduct formed by contacting an amine with CO2, and at least one of these chemical elements.
• the invention also relates to a kit for implementing the method of detection, capture and / or release.
• the mixed rare earth concentrates are obtained after several steps of separation of the extracted ores to obtain very high levels of purity.
• Rare earth concentrates can also be obtained from post-consumer waste by specialized recyclers.
• the methods of selective sorting of this type of elements rely mainly on countercurrent liquid / liquid extraction processes, after the ion chromatography and the selective precipitation have been abandoned. These methods are expensive in terms of infrastructure, time and energy, with low capacity and performance.
• a new separation approach that can significantly reduce operational and infrastructure costs compared to the liquid-liquid separation technology used in the rare earth industry has been developed.
• a first object of the invention is a method for detecting and / or capturing at least one chemical element chosen from the poor metals, the alkalis, the alkaline earth metals, the actinides and the rare earths in a sample, comprising contacting:
• At least one amine and at least one aldehyde and / or imine formed by contacting an aldehyde with an amine) and / or CO2, or
• a second subject of the invention is a method for the release of at least one chemical element chosen from poor metals, alkalis, alkaline earth metals, actinides and rare earths comprising at least partial, preferably total, separation of components of an assembly formed by contacting:
• a third subject of the invention is a method for forming a molecular assembly comprising contacting:
• At least one amine and at least one aldehyde and / or imine formed by contacting an aldehyde with an amine) and / or CO2, or
• a final subject of the invention is a kit for detecting, capturing and / or releasing at least one chemical element chosen from the poor metals, the alkalis, the alkaline earth metals, the actinides and the rare earths, comprising at least one amine, and at least one aldehyde and / or imine and / or CO2, or an adduct formed by contacting an amine and CO2.
• Figure 1 Analysis of libraries made without adding CO2, after 15 minutes and 2880 minutes. Each cell corresponds to the combination of an amine on the abscissa and an aldehyde or an imine on the ordinate. A gray box corresponds to the observation of a precipitate proving the formation of an assembly.
• FIG. 2 Analysis of the libraries realized in the presence of CO2, after 15 minutes and 2880 minutes. Each cell corresponds to the combination of an amine on the abscissa and an aldehyde or an imine on the ordinate. A gray box corresponds to the observation of a precipitate proving the formation of an assembly.
• the methods for detecting, capturing and / or releasing the chemical elements according to the invention are based on the formation of molecular assemblies when the chemical elements are brought into contact with at least one amine, and at least one aldehyde and / or or an imine and / or C0 2 , or with an adduct formed by contacting an amine and CO2.
• the formation of such an assembly is detected by the formation of a precipitate within the medium comprising the various components.
• the invention relates to a method for detecting and / or capturing at least one chemical element selected from alkalis, alkaline earths, actinides and rare earths in a sample, comprising contacting the at least one amine, at least one aldehyde and / or imine, optionally CO2, and optionally an adduct formed by contacting an amine and CO2, and at least one of said chemical elements.
• An aldehyde according to the invention is a compound comprising at least one aldehyde function CHO.
• the aldehyde can be of general formula
• R1 is selected from alkyl, alkenyl, acynyl, cycloalkyl, cycloalkenyl, cycloalkynyl and aromatic groups, wherein the hydrocarbon chain is optionally interrupted by at least one heteroatom selected from N, O and S, and optionally substituted with at least one a substituent.
• the substituents do not independently comprise amine (-NHR or -NH 2 ), hydrazine (-NH-NH 2), hydrazide (C (O) -NH-NH 2 ), or hydroxy lamin (-O-NH 2).
• the substituents are as defined below.
• the aldehyde is of general formula
• L 1 - 1 represents a hydrocarbon ring chosen from cycloalkyls, cycloalkenes, cycloalkynes and aromatics, comprising n chain members, n being between 5 and 7, preferably n is 5 or 6.
• the hydrocarbon ring is a phenyl.
• the hydrocarbon ring may optionally be interrupted by at least one heteroatom chosen from N, O and S.
• Each substituent R n is chosen from a hydrogen atom, an aldehyde CHO, a hydroxyl group -OH, a thiol -SH, an atom halogen, an alkoxyl group, and a C 1 -C 20, preferably C 1 -C 3, alkyl.
• each alkyl group does not independently comprise any amino substituent (-NHR or -NH 2 ), hydrazine (-NH-NH 2), hydrazide (C (O) -NH-NH 2 ), or hydroxylamine (- O-NH2).
• At least one R n comprises, preferably is, a CHO aldehyde.
• an alkyl group denotes a hydrocarbon group, linear or branched C 1 -C 20 , preferably C 1 -C 6 , in particular C 1 -C 3 .
• the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl.
• the alkyl group may optionally be interrupted by at least one heteroatom chosen from N, O and S.
• the alkyl group may optionally be substituted, in particular with at least one group chosen from hydroxyl (-OH) and alkoxyl (-OR) groups.
• An alkynyl group denotes an alkyl group, as defined above, further comprising at least one C tripleC triple bond.
• the cycloalkyl, cycloalkenyl and cycloalkynyl groups respectively represent cyclic alkyl, alkenyl and alkynyl groups.
• An aromatic is a group comprising at least one plane ring comprising a conjugated ⁇ system, formed of double bonds and / or non-binding pairs, in which each ring atom has a p orbit, the p orbital overlap, and the delocalization ⁇ electrons cause a decrease in the energy of the molecule.
• an aromatic is selected from phenyl, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl and naphthyl.
• the aromatic group is phenyl.
• alkoxyl group denotes an alkyl group as defined above, said alkyl group being connected to the remainder of the molecule via an oxygen atom.
• Halogen denotes an atom selected from fluorine, bromine, chlorine and iodine, preferably chlorine or bromine.
• the aldehyde is of formula (III) wherein at least one of R 1 to R e is an aldehyde group, and the others are selected from hydrogen atoms, C 1 -C 20 alkyl groups, hydroxyl groups, thiol groups, halogen atoms, and C1-C20 alkoxyl groups.
• the aldehyde is selected from the following compounds:
• the aldehyde is chosen from compounds B and C, in particular the aldehyde is the compound C.
• aldehydes according to the invention can be obtained by any suitable synthetic route known in the art.
• certain aldehydes of the invention may be obtained by reaction of Duff with hexamethylenetetramine.
• An amine according to the invention is a compound comprising at least one, preferably one or two, primary amine -NH 2 or secondary -NHR function, where R is as previously described, and optionally at least one tertiary amine function.
• the amine according to the invention can be of general formula (IV) R 2 -NH-R 3, in which R 2 is chosen from alkyl, alkenyl, acynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups and aromatic groups, whose hydrocarbon chain is optionally interrupted by at least one heteroatom selected from N, O and S, and optionally substituted by at least one substituent as defined above, which substituent preferably does not comprise CHO aldehyde; R3 is chosen from a hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl groups and aromatic groups, the hydrocarbon chain of which is optionally interrupted by
• the amine comprises a single amine function.
• the amine comprises at least 2 amino functions, preferably at least 3, at least 4, or at least 5 amino functions.
• the amine is such that R3 is a hydrogen atom and R2 is an alkyl group whose hydrocarbon chain is interrupted by at least one nitrogen atom.
• the method according to the invention comprises bringing into contact, in particular, an amine comprising at least two amino functions, and an imine formed by reaction of an aldehyde with an amine comprising a single amine function. .
• the method according to the invention comprises contacting in particular an amine comprising at least 2 amine functions, and an adduct formed by reaction of an amine comprising a single amine function with the C0 2 .
• an amine according to the invention is chosen from the following compounds:
• aminoethyl) amine 2 a polyethyleneimine, in particular a linear or branched polyethyleneimine, in particular diethylenetetramine , the piperazm trans-1,4-
• the amine is selected from ethylenediamine, diethylenetriamine 2, triethylenetetramine 6 and tris- (2-aminoethyl) amine.
• the amine is compound 2.
• the aldehydes and amines of the invention are chosen by those skilled in the art according to their structural characteristics, for example the number of reactive functions (aldehydes and / or amines) and / or the molar mass.
• the formation of the assemblages involves the formation of imine bonds, by reaction of the amino groups of the amines with the aldehyde groups of the aldehydes. Hydrazone, oxime, aminal, oxazolidine, thiazolidine and / or carbamate type bonds may also be involved.
• an imine according to the invention is obtained by contacting an aldehyde according to the invention with an amine of formula (IV) as defined above.
• the amine comprises a single amine function.
• R 2 is an unsubstituted hydrocarbon alkyl group comprising only single bonds and R 3 is a hydrogen atom, in particular the amine is n-butylamine.
• all the CHO groups of the aldehyde according to the invention react with the amine.
• only certain CHO groups of the aldehyde react with the amine.
• an imine according to the invention may comprise both CHO groups and imine groups.
• an imine according to the invention is chosen from the following compounds:
• the imine is chosen from the compounds AI3 and BI3, in particular the polyimine is the compound BI3.
• An adduct according to the invention is obtainable, preferably it is obtained by bringing an amine according to the invention into contact with carbon dioxide.
• the adduct may be a carbamate.
• the adduct may also be an aminal (If the amine is an ethanediamine or propanediamine), an oxazolidine (if the amine is an aminoethanol or an aminopropanol), or a thiazolidine (if the amine is an aminoethanethiol or an aminopropanethiol).
• An assembly formed according to the process of the invention may optionally comprise carbon dioxide.
• the carbon dioxide used may be from a human activity of which it represents a waste, for example it may come from combustion fumes, refinery gas, cementery gas or blast furnace gas.
• the assembly formed according to the method of the invention comprises at least one chemical element chosen from poor metals, alkalis, alkaline earths, actinides and rare earths.
• poor metals denote the metal elements of the group p of the periodic table.
• the group of the poor metals includes Aluminum 13AI, Gallium 3iGa, Indium 49m, Tin SoSn, Thallium 8iTl, Lead 8 2 Pb, Bismuth 83B1, Polonium 84P0 and Flérovium 114 F1.
• the lean metal is indium.
• the alkalis denote the elements of the first column of the periodic table, with the exception of hydrogen.
• the alkali group includes 3L1 lithium, nNa sodium, 19K potassium, rubidium 37Rb, cesium 55CS and 87Fr francium.
• the alkali metal is cesium.
• the alkaline earths designate the elements of the second column of the periodic table.
• the alkaline earth group includes 4 B beryllium, 12 Mg magnesium, 2 oCa calcium, 3sSr strontium, 6 6 Ba barium and ssRa radium.
• actinides denote actinium 8 Ac, thorium 9oTh, protactinium 9iPa, uranium 92U, neptunium 93NP, plutonium 9 4 Pu, americium 9 5 Am, curium 9ôCm , Berkelium 97Bk, California 9sCf, Einsteinium 99ES, Fermium 10mFm, Mendonulvium n'Md, Nobelium 102N0, and Lawrencium io3Lr.
• the actinides are selected from thorium and uranium.
• the rare earths denote scandium 21 Se, yttrium 39Y and the fifteen lanthanides.
• Lanthanides designate the 57La lanthanum, SSCE cerium, praseodymium 59Pr, neodymium 6 OND 6iPm promethium, samarium 62Sm, europium 63Eu, gadolinium Gd 64, 65Tb terbium, dysprosium Dy 6 6, the holmium 67H0, erbium 6 sEr, thulium 69Tm, ytterbium 70 Yb and lutetium 7iLu.
• the rare earths include lanthanum and / or lutetium.
• At least one of the chemical elements is rare earth (s), in particular La and / or Lu.
• the chemical element can be contacted with the other components in the form of element without bond to another atom, or in the form of a derivative, such as a salt or a complex.
• the element can be brought into contact with the other components in the form of a nitrate, a trifluoroacetate or an acetate.
• the sample on which the method of detection and / or capture according to the invention is implemented may be any type of sample capable of comprising one or more chemical elements as defined above. It can be a sample of any origin.
• the amounts (absolute or relative) of the various components of the assembly formed according to the method of the invention may be adapted by those skilled in the art so as to optimize the formation of the assembly.
• the skilled person is able to adjust the relative proportions of aldehyde and amine, in the case where these two types of components are part of the desired assembly, so that the ratio between the number of aldehyde functions and the number of amino functions brought into from about 0.1 to about 10, preferably from about 0.8 to about 1.2, in particular about 1.
• the ratio between the number of moles of amine and the number of moles of the element that one seeks to detect and / or capture is greater than or equal to 6, preferably greater than or equal to
• it seems that such a ratio makes it possible to confer thermal reversibility properties on the precipitate which forms in the presence of the chemical element.
• the ratio values between the number of moles of amine and the number of moles of the element which one seeks to detect and / or to capture making it possible to obtain such a thermal reversibility may possibly vary as a function of the counter-ion.
• the chemical element that is to be detected and / or captured such as nitrate, acetate, or trifluoroacetate.
• the term "about” relative to a numerical value refers to an interval between minus and plus 10% of said numerical value.
• the method for detecting and / or capturing the chemical elements according to the invention comprises bringing into contact with:
• At least one amine and at least one aldehyde and / or imine formed by placing an aldehyde in contact with an amine) and / or C0 2 , or
• the method comprises contacting at least one amine and CO 2 , or an adduct formed by contacting an amine and CO2, with said sample.
• the contacting can be carried out by any suitable technique known in the art.
• the contacting is carried out at room temperature, that is to say between about 15 and about 25 ° C.
• the process may optionally further comprise a step of heating the mixture obtained at a temperature higher than that of the contacting, preferably at a temperature of between 26 and 100 ° C., in particular at a temperature in the region of 90 ° C. .
• the method also further comprises a step of controlled cooling of the mixture to ambient temperature as defined above.
• a precipitate can be obtained during contacting at room temperature and / or during cooling at the end of the process.
• thermodynamic stability criteria and / or kinetics of this- this.
• exchanges are favored and the assembly can self-organize according to the most stable arrangement if the temperature drop is slow, which should also allow capturing larger quantities of chemical elements.
• Contacting can be carried out with or without mechanical or magnetic stirring, and preferably in a controlled atmosphere, for example under an argon inert atmosphere.
• the controlled atmosphere preferably comprises CO 2, in particular it is a CO 2 atmosphere.
• the contribution of CO2 can also be made by bubbling CO2 into the liquid medium comprising the other components and the sample that may comprise a chemical element as defined above, by adding a carbonate salt and / or hydrogencarbonate, and / or by adding dry ice to said liquid medium.
• the medium comprising the various components and the sample that may comprise a chemical element as defined above is preferably a liquid medium.
• the bringing into contact of the different components can be carried out either sequentially or simultaneously.
• contacting the amine, aldehyde and / or imine and / or CO2, or the adduct formed by contacting an amine and CO2 with the sample likely to understand the chemical element is simultaneous.
• the term "simultaneous" means that the bringing into contact of the different components is performed in a short period of time, for example between 0 and 30 minutes. In particular, it is of the order of less than 15 minutes, less than 10 minutes, less than 5 minutes, less than 2 minutes or less than one minute.
• the addition of the sample likely to comprise the chemical element is made less than 2 minutes after the mixing of the other components.
• the order in which the components are added may be any, and one skilled in the art is able to determine the most appropriate order depending on the nature of each of the components.
• the sample likely to comprise the chemical element is added after the other components of the assembly.
• the contacting of the different components may optionally be carried out in the presence of other compounds, for example in the presence of at least one solvent.
• the solvent may be chosen from any organic or aqueous solvent and adapted to the components contacted, for example to promote their dissolution.
• the solvent is chosen from alcohols, for example it is ethanol or methanol.
• the solvent can be used in anhydrous form or at different degrees of hydration.
• the formation of the assembly according to the invention is visualized by the appearance of a precipitate, which can be easily separated from the reaction medium, for example by simple filtration and / or centrifugation.
• the step of detecting and / or capturing the chemical elements of the process according to the invention is therefore performed by observing this precipitate after contacting the various components.
• the detection step further comprises comparing the sample obtained with a similar sample which does not include the chemical element, and which may be named reference sample.
• the detection step may further include comparing the resulting sample with a similar sample that includes the chemical element.
• the detection of the presence (or absence) of the element to be detected and / or captured is validated by the appearance of a precipitate in the case where the element is present, and the absence of precipitate under the same conditions in the case where the element is absent.
• the detection and / or capture method according to the invention can be used to determine the absence, presence and / or quantity (absolute or relative) of at least one chemical element in a sample.
• the detection and / or capture method according to the invention optionally comprises a step of separating the formed molecular assembly which precipitates.
• the separation step can be performed by any suitable technique known to those skilled in the art.
• the separation can be carried out by decantation, filtration, sieving, centrifugation, evaporation and / or distillation.
• the separation step is carried out by simple filtration and / or centrifugation.
• the skilled person is able to adjust the parameters of the chosen technique to obtain optimal separation.
• it is able to adjust the filtration parameters, such as the nature of the filter and / or the pore size, and / or the centrifugation parameters, such as the centrifugation speed, at the assembly and the sample concerned, to obtain optimal separation.
• the sample on which the method of detection and / or capture according to the invention is implemented may be any type of sample capable of comprising one or more chemical elements as defined above.
• the sample may be in gaseous, liquid or solid form, preferably it is in liquid or solid form.
• the detection method and / or capture according to the invention does not lead to the formation of an assembly or the observation of a precipitate.
• the method according to the invention is a method for detecting the absence in the sample of at least one of the chemical elements targeted. This sample may be named reference sample.
• the method of detection and / or capture according to the invention is carried out within a dynamic combinatorial library comprising at least one amine and at least one aldehyde and / or imine and / or C0 2 or an adduct formed by contacting an amine and CO2 according to the invention.
• the method of detection and / or capture according to the invention has undeniable advantages over current detection and / or capture techniques.
• the capture method according to the invention does not necessarily involve high temperatures, and the process can be advantageously carried out at room temperature.
• metallurgical processes are generally carried out at temperatures of several hundred degrees.
• the "molecular bricks" that constitute the assemblies that is to say the aldehydes, imines and / or amines are simple compounds, sometimes commercial, which do not require custom synthesis.
• the separation process involves as simple separation step a simple phase separation, for example by filtration or centrifugation, much simpler and economic to implement that other separation techniques conventionally used in this field, such as extractions or chromatographies, which consume in addition large amounts of solvent.
• the method according to the invention can allow, especially after re drop, the recycling and / or reuse of at least some of the "molecular bricks" that constitute the assemblies. This possibility of reusing the components makes it possible to limit or even eliminate the effluents leaving the process.
• the assemblies according to the invention can use as capture agent carbon dioxide, which is a waste.
• the process according to the present invention is clearly economical and energy-saving, which represents major industrial assets.
• an assembly according to the invention can be selectively formed with only one type of chemical element. For example, separation factors up to 20 could be obtained for the separation of two rare earths, such as for example La and Lu, in the same sample by implementing a method according to the invention.
• the detection and / or capture of at least one chemical element according to the method of the invention is selective of a chemical element.
• Another object of the invention is a method of releasing the captured element (or captured elements) in the assembly, by separation or dissociation, at least partial, preferably total, of the components of the assembly.
• This separation can be carried out, for example, by heating, preferably at a temperature of less than or equal to 100 ° C., or by hydrolysis, in particular by acidic hydrolysis, basic hydrolysis or in at least a neutral neutral buffered medium of the assembly.
• the separation of the components of the assembly makes it possible to release and / or reform at least some of the components, preferably all the components, of the assembly.
• the separation makes it possible to release and / or reform at least one component, preferably all of the aldehydes, imines, amines and / or CO2 forming the assembly, or a derivative thereof.
• the term "one of their derivatives" refers to a chemical derivative of the aldehyde or amine, from which one skilled in the art knows how to reform the aldehyde, or the amine.
• the release process may make it possible to release an aldehyde in the case where an imine had been used to form the assembly.
• the salting out process may further comprise after hydrolysis a step of removing the aqueous solution obtained, to allow the re-use of the components.
• the chemical element (s) chosen from the poor metals, the alkalis, the alkaline earth metals, the actinides and the rare earths are released either in the form of a chemical element or in the form of a derivative comprising the chemical element, for example in the form of a complex or a salt.
• Another object of the invention is a method of forming a molecular assembly comprising contacting:
• At least one amine and at least one aldehyde and / or imine formed by placing an aldehyde in contact with an amine) and / or CO2, or
• At least one sample comprising at least one chemical element selected from poor metals, alkalis, alkaline earth metals, actinides and rare earths.
• the molecular assembly formed by this process is also an object of the invention.
• kits comprising at least one amine, and at least one aldehyde and / or imine and / or CO2, or an adduct formed by bringing an amine and CO2 into contact, these components being as defined above.
• This kit is particularly suitable for the detection, capture and / or release of at least one chemical element according to the invention.
• the kit may comprise at least two aldehydes and / or imines and / or at least two amines.
• the kit may especially be in the form of a support adapted for use in dynamic combinatorics, said support comprising several wells, in which each well comprises at least one amine and optionally at least one aldehyde and / or imine.
• the support may for example be a plate comprising wells.
• yield refers in the present invention to a magnetic yield.
• the aldehyde D was synthesized according to the following reaction
• the aldehyde E was synthesized according to the following reaction:
• Imines Al 3 and BI 3 were formed by reaction of aldehydes B and C with n-butylamine, according to the following reaction:
• the lanthanum, gadolinium and lutetium salts were prepared from oxides heated under reflux for 12 hours in a mixture of trifluoroacetic acid and water.
• Lu (CF3COO) 3 0.5 g of Lu 2 O 3 are suspended in 8 ml of distilled water, then 10 ml of trifluoroacetic acid are added dropwise. The mixture is stirred at 110 ° C overnight. The solution is sintered and the filtrate is evaporated on a rotary evaporator. The solid obtained is taken up three times with ethanol. The salt (1 g) is obtained after vacuum drying in the form of a white powder with a yield of 90%.
• Gd (CF3COO) 3 5 g of Gd 2 0 3 are suspended in 80 ml of distilled water, then 100 ml of trifluoroacetic acid are added dropwise. The mixture is stirred at 110 ° C overnight. The solution is sintered and the filtrate is evaporated on a rotary evaporator. The solid obtained is taken up three times with ethanol. The salt (11 g) is obtained after vacuum drying in the form of a white powder with a yield of 90%.
• the indium nitrates In (NO 3 ) 3 , neodymium Nd (NO 3 ) 3 of praseodymium Pr (NO 3 ) 3 and lutetium Lu (NO 3 ) 3 were respectively obtained by etching of indium oxide. , neodymium, praseodymium and lutetium with nitric acid. 1 g of corresponding oxide is dispersed in 20 ml of distilled water, 10 ml of 68% nitric acid are added. The mixture is heated under reflux until the oxide is completely dissolved, and after returning to ambient temperature, the solution is filtered. The nitrate salt is obtained after complete evaporation of the solvent and drying with the paddle pump.
• Pr (CH 3 CO 2 ) 3 and lutetium Lu (CH 3 CO 2 ) 3 were obtained respectively by etching indium, neodymium, praseodymium and lutetium oxide with acetic acid. 1 g of corresponding oxide is dispersed in 20 ml of distilled water, 20 ml of 68% nitric acid are added. The mixture is heated under reflux until the oxide is completely dissolved, and after returning to ambient temperature, the solution is filtered. The nitrate salt is obtained after complete evaporation of the solvent and drying with the paddle pump.
• the different libraries were prepared by mixing one equivalent of aldehyde (or imine), one equivalent of metal salt, and two equivalents of amine.
• the final concentration in the libraries is 20mM aldehyde or imine, 20mM metal salt and 40mM amine.
• the libraries were placed under an atmosphere of C0 2 or argon. The libraries have been duplicated three times.
• FIGS. 1 and 2 include the analysis of the libraries for each of the conditions tested, for the two experiment times of 15 minutes and 2880 minutes.
• the shaded boxes in the tables correspond to the experiments for which a precipitate (characteristic of the formation of an assembly according to the invention) could be observed. It is clear that bringing into contact, according to the invention, an aldehyde or an imine, an amine, optionally carbon dioxide, and a chemical element chosen from lanthanum and lutetium has allowed forming an assembly according to the invention in a large number of conditions.
• the libraries were prepared by mixing one equivalent of aldehyde (or imine), one equivalent of lanthanum salt, one equivalent of lutetium salt and two equivalents of amine.
• the final concentration in the libraries is 20mM aldehyde (or imine), 20mM lanthanum, 20mM lutetium and 40mM amine.
• the final volume of the library is 6 mL.
• the precipitates were separated as soon as the presence of a precipitate was observed. The results of the elemental analysis of the precipitates obtained are summarized in Table 1 below.
• Table 1 Elemental analysis of the precipitates obtained The elemental analysis confirms the presence of lanthanides in the precipitates, thus a capture of the metal ions during the formation of the precipitates. In addition, the elemental analysis shows (see column La / Lu ratio) that certain conditions, in particular solids prepared in the presence of CO 2 and aldehyde C, have a selectivity of interest with respect to Lutetium.
• the operating mode implemented is as follows:
• Ratio of the committed masses mM / (m 5 + mB + mNHBu + mco2 max + mM) with mM ° the mass of introduced metal, ms ° the mass of introduced spermidine, mc ° the mass of introduced aldehyde, niNHBu 0 the mass of butylamine introduced and mco 2 max the maximum mass of CO2 that can be captured.
• ICP-MS refers to plasma torch mass spectrometry.
• Solids obtained in the presence of 1 and 0.5 equivalents of Lanthanum and Lutetium were analyzed by LC-MS.
• Libraries with 1 equivalent of La and Lu were prepared by mixing 1 mL of 60 mM aldehyde, 1 mL of 120 mM amine, 500 ⁇ L of La (CF 3 COO) 3 at 120 mM and 500 ⁇ of Lu (CF). 3 COO) 3 to 120 mM.
• Libraries with 0.5 equivalents of La and Lu were prepared by mixing 1 mL of 60 mM aldehyde, 1 mL of 120 mM amine, 250 ⁇ L of La (CF 3 COO) 3 at 120 mM, 250 ⁇ L of Lu (CF). 3 COO) 3 to 120 mM and 500 methanol.
• Example 4 Capture of different elements with the polethyleneimine Operating modes:
• the PEI allowed the capture of In, Pr and Lu.
• the metal contents in the analyzed solids are low (less than 1%). However, they are of the same order of magnitude as the mass ratio of PEI on mass of metal used for capture and are consistent with the increase in mass of the polymer by absorption of CO2.
• the solids obtained by slow precipitation (temperature decrease at from 90 ° C) have a higher metal content than the solids obtained by capture at room temperature.
• the selectivity between Pr and Lu is in favor of Lu with a Pr / Lu ratio of 0.75.
• Engaged mass ratio mM / (nu + mco2 max + mM) with the mass of metal introduced, n 0 the mass of amine introduced and mco2 max the maximum mass of CO2 that can be captured with a mass of 0 d Amine engaged.
• the capture is more efficient at 90 ° C in the case of linear amines (En, DETA, TETA) and is more effective at TA in the case of Tren.
• the ICP-MS measurement shows that this system allows the reversible capture of In from a solution in alcohol.

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• Engineering & Computer Science (AREA)
• Biophysics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Gas Separation By Absorption (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
• Manufacture And Refinement Of Metals (AREA)

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• 2013
  • 2013-05-20 FR FR1354510A patent/FR3005741B1/fr not_active Expired - Fee Related
• 2014
  • 2014-05-20 WO PCT/FR2014/051172 patent/WO2014188115A1/fr not_active Ceased
  • 2014-05-20 CA CA2912795A patent/CA2912795C/fr active Active
  • 2014-05-20 EP EP14731694.7A patent/EP2999962B1/fr active Active
  • 2014-05-20 SI SI201430190T patent/SI2999962T1/sl unknown
  • 2014-05-20 JP JP2016514459A patent/JP6312813B2/ja active Active
  • 2014-05-20 US US14/892,317 patent/US10571449B2/en active Active
  • 2014-05-20 CN CN201480038732.8A patent/CN105579845B/zh active Active

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