Patent Application
20230398517
The subject matter of the present invention consists of formo-phenolic resins, a method for the preparation thereof, and the use of same in the extraction of uranium from an aqueous sample.
According to the IAEA (International Atomic Energy Agency), the world's nuclear power plant should increase from a capacity of approximately 377 GWe at the beginning of 2015 to a capacity of between 418 GWe and 683 GWe by 2035.
Consequently, the demand for uranium is expected to increase, requiring the search for new potentially exploitable resources.
One possible solution is the recovery of the uranium present in aqueous samples, particularly in seawater.
Indeed, although uranium is present in low concentration in seawater, on average at 3.3 pg/L, it is still the largest uranium resource on Earth with about 4.5 billion tons exploitable, about 500 times more than terrestrial uranium.
However, the low concentration of uranium in seawater is accompanied by the presence of other metals, such as sodium, potassium, magnesium, calcium and strontium in higher concentrations.
The first studies dealing with the recovery of uranium from seawater date from the early 1960s. Adsorption by chelating materials appears to be the most promising method for the recovery of uranium from seawater, in terms of operating simplicity, operating cost, environmental risk and storage capacity. adsorption.
In this context, formo-phenolic resins have for example been developed.
These resins can be formed by reacting phenol with formaldehyde. Examples of commercially available formo-phenolic resins are Resol and Novolac (L. Pilato (ed.), Phenolic Resins: A Century of Progress, Springer-Verlag Berlin Heidelberg 2010).
However, the materials developed to date have weaknesses in the context of their use in the extraction of uranium from a water sample, in particular a low selectivity towards competing metals.
There is therefore a real challenge in developing new materials with a very strong affinity for uranium and a very good selectivity towards several metals from seawater solution.
One of the aims of the invention is the use of formo-phenolic resins for the extraction of uranium, in particular from sea water.
One of the other objects of the invention is the provision of a method for the preparation of formo-phenolic resins.
One of the other aims of the invention is the provision of new formaldehyde-phenolic resins.
One of the other objects of the invention is to provide a method for extracting uranium from a water sample.
One of the other aims of the invention is to be able to extract uranium from a water sample with good selectivity with respect to other metals.
A first object of the present invention is the use of a crosslinked formo-phenolic resin for the extraction of uranium from an aqueous solution, in particular seawater, said resin being insoluble in an aqueous medium at a pH comprised from 3 to 10, in particular from 5 to 8, said resin consisting of a polymer containing monomer units linked together by one or more group(s) —R″—wherein R″ represents a —(CH2)— group, a linear or branched-(CH)—C1-C10-alkyl group, a —(CH)— aryl group, a —(CH)-heteroaryl group, a linear or branched —(CH)—(C1 to C10) alkylaryl group, a linear or branched-(CH)—(C1-C10-alkyl)heteroaryl, a-(CH)-aryl-(CH)— group, a linear or branched-(CH)—(C1 to C10-alkyl)-aryl-(C1 to C10-alkyl)-(CH)-group, a-(CH)-heteroaryl-(CH), a linear or branched (CH)—(C1 to C10-alkyl)-heteroaryl-(C1 to C10-alkyl)-(CH)-group, said monomer units being:
The inventors have surprisingly found that the resins according to the present invention, used in a method for extracting uranium, have remarkable and unprecedented extraction properties, in terms of selectivity, and in terms of ability to extraction.
A “cross-linked formo-phenolic resin”, within the meaning of the present invention, is a resin which may be the result of a reaction of monomers of Formula 1, and/or of monomers of Formula 6, and/or of monomers of Formula 7, with an aldehyde. A cross-linked structure is then formed, similar to that found in Resol or Novolac resins.
The expression “formo-phenolic” is therefore not limited to a resin based on formaldehyde and phenol, but this expression refers to resins based on any aldehyde that can lead to the —R11-group as defined above. above, and the monomers as defined above.
The resins according to the present invention may, by way of example, and depending on the substitution pattern, comprise the following structural elements:
In this case, element 1 is included in a resin containing monomer units of Formula 7, wherein the R16 substituent represents an —OH group, and the R13 and R5 substituents represent a hydrogen atom.
In the resin, one or more of the R13 and R15 substituents no longer represent a hydrogen atom because the hydrogen atoms have been replaced by the —R″-group
The expression “at least two of the R11 to R16 substituents represent a hydrogen atom,” therefore refers to the monomer units used as raw material in the formation of the resins according to the invention.
It is understood that, in the definition of the group R″, a —(CH)-alkyl group, a —(CH)-aryl group, a —(CH)-heteroaryl group, a —(CH)-alkyl aryl group, or a —(CH)-alkyl aryl group, is a group wherein the radical (CH) is attached to the monomers by two carbon-carbon bonds, as exemplified below for the particular case of —(CH)-alkyl.
It is also understood that, in the definition of the group R11, a —(CH)-aryl-(CH)— group, a —(CH)— (alkyl-aryl-alkyl)-(CH)— group, a —(CH)-heteroaryl-(CH)-group, a (CH)-alkyl-heteroaryl-alkyl)-(CH)— group, the two radicals (CH) are attached to the monomers by two carbon-carbon bonds, as exemplified below for the particular case of —(CH)-aryl-(CH)—
This configuration is obtained by the use of a dialdehyde in the preparation of the resin. By “linear C1 to C10 alkyl group” is meant: a C1 methyl group, a C2 ethyl group, a C3 n-propyl group, a C4 n-butyl group, a C5 n-pentyl group, a C6 n-hexyl group, a C7 n-heptyl group, a C8 n-octyl group, a C9 n-nonyl group, or a C10 n-decyl group.
By “branched alkyl group”, it is necessary to understand a linear alkyl group as defined above comprising substituents chosen from the linear alkyl groups defined above, said linear alkyl groups also being able to be branched. Among the branched alkyl groups, mention may in particular be made of a group iso-propyl, sec-butyl, iso-butyl, tert-butyl, sec-pentyl, iso-pentyl, iso-hexyl, iso-heptyl, iso-octyl, iso-nonyl and iso-decyl.
By “linear C1 to C10 heteroalkyl group”, it is meant: a linear alkyl chain of 1 to 10 carbon atom(s), in particular of 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atom(s), in particular from 2 to 10, or from 5 to 10 carbon atoms, comprising one or more heteroatoms, in particular chosen from O, S, N or NO in particular 1, 2, 3, 4 or 5 heteroatoms.
Mention may in particular be made of a chain based on ethylene glycol or ethylene amine. The linear heteroalkyl group is in particular a group —O-linear C1 to C10 alkyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, or a group —NH-linear C1 to C10 alkyl, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, or a linear —S—C1 to C10 alkyl group, methyl mercaptan, ethyl mercaptan, n-propylmercaptan, n-butylmercaptan, n-pentylmercaptan, n-hexylmercaptan, n-heptylmercaptan, n-octylmercaptan, n-nonylmercaptan,
By “branched heteroalkyl group”, it is necessary to understand a heteroalkyl group as defined above comprising substituents chosen from the groups of linear alkyls or linear heteroalkyls defined above, the said linear alkyl or linear heteroalkyl groups also being capable to be branched.
The branched heteroalkyl group is in particular a branched C3 to C10-O-alkyl group, such as for example iso-propoxy, sec-butoxy, iso-butoxy, tert-butoxy, sec-pentoxy, iso-pentoxy, iso-hexoxy, iso-heptoxy, iso-octoxy, iso-nonoxy ou iso-decoxy, or a branched-NH—C3 to C10 alkyl group, such as for example iso-propylamine, sec-butylamine, iso-butylamine, tert-butylamine, sec-pentylamine, iso-pentylamine, iso-hexylamine, iso-heptylamine, iso-octylamine, iso-nonylamine ou iso-decylamine,
By “C3 to C10 cycloalkyl group” is meant: a C3 cyclopropyl group, a C4 cyclobutyl group, a C5 cyclopentyl group, a C6 cyclohexyl group, a C7 cycloheptyl group, a C8 cyclooctyl group, a C9 cyclononyl group, or a C10 cyclodecyl group.
A “branched cycloalkyl group” denotes a cycloalkyl group as defined above, said cycloalkyl group being substituted, in particular by a linear or branched, C1 to C10 alkyl group as defined above.
The term “aryl” denotes an aromatic group comprising 5 to 16 carbon atoms within the aromatic ring, in particular from 6 to 12 carbon atoms, in particular comprising 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 carbon atoms. The aryl groups according to the present invention can also be substituted, in particular by one or more substituents chosen from: a linear or branched C1 to C10 alkyl group, a linear or branched C1 to C10O-alkyl group.
Phenyl, toluyl, anisyl and naphthyl o-tolyl, m-tolyl, p-tolyl, o-xylyl, m-xylyl, p-xylyl, are examples of aryl groups according to the present invention.
The term “heteroaryl” denotes an aryl group as defined above, comprising atoms other than carbon atoms, in particular N, O or S within the aromatic ring.
Pyridyl, imidazoyl, or furanyl are examples of heteroaryl groups according to the present invention.
By way of non-limiting example, the phenolic monomer of Formula 7 can be chosen from phenol, catechol, resorcinol, hydroquinone, hydroxyquinol, phloroglucinol, pyrogallol, benzenetetrol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-acid dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, a-resorcylic acid, pyrogallolcarboxylic acid, 2,3,5-trihydroxybenzoic acid, 2,3,6-trihydroxybenzoic acid, acid 2,4,5-trihydroxybenzoic acid, phloroglucinic acid, gallic acid, 4-hydroxybenzene phosphonic acid, 1,2-dihydroxybenzene phosphonic acid, 3,4-dihydroxybenzene phosphonic acid, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,3-difluorophenol, 2,4-difluorophenol, 2,5-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 2,3,4-trifluorophenol, 2,3,6-trifluorophenol, 2,4,6-trifluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 2,3,4- trichlorophenol, 2,3,6-trichlorophenol, 2,4,6-trichlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,3-dibromophenol, 2,4-dibromophenol, 2,5-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 2,3,4-tribromophenol, 2,3,6-tribromophenol, 2,4,6-tribromophenol, bisphenol A, o-phenylphenol, m-phenylphenol, p-phenylphenol, 4-hydroxybenzo-18-crown-6,6-hydroxybenzo-15-crown-5,4-hydroxybenzo-18-crown-6,6-hydroxybenzo-18-crown-6. calix[4]resorcinarene, calix[4]hydroquinone, calix[4]arene, calix[6]arene, calix[8]arene and mixtures thereof.
The chelating monomers of Formula 1 preferably have 2, 3 or 4 R1 to R5 substituents which represent a hydrogen atom,
The chelating monomers of Formula 6 preferably have 2, 3 or 4 R6 to R10 substituents which represent a hydrogen atom,
Monomers of Formula 7 preferably have 3 or 4 R11 to R16 substituents which represent a hydrogen atom.
According to another particular embodiment, the present invention relates to the use as defined above, wherein said resin consists of a polymer containing said monomer units linked together by one or more —(CH2)-group(s) or by one or more —(CH2)—CH3 group(s).
It is respectively a resin based on formaldehyde, or based on acetaldehyde.
According to another particular embodiment, the present invention relates to the use as defined above, wherein said resin consists of a polymer containing said monomer units linked together by one or more —(CH2)-group(s).
According to this preferred embodiment, the monomer units of Formula 1 and/or of Formula 6 and/or of Formula 7 are linked together by one or more —(CH2)-group(s).
It is a formaldehyde-based resin, or a resin that can be obtained by reacting said monomer units with formaldehyde.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units are of Formula 1,
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units are of Formula 1,
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units are of Formula 6,
According to another particular embodiment, the present invention relates to the use as defined above,
According to another particular embodiment, the present invention relates to the use as defined above, wherein the monomer units are of Formula 7,
According to another particular embodiment, wherein the monomer units are of Formula 7, wherein:
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units of Formula 1 have the structure of Formula 8:
L and q being as defined above.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units of Formula 1 have the structure chosen from the structures of Formula 10, of Formula 11, and of Formula 12:
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units of Formula 6 have the structure of Formula 19:
L, q, R8, R9 and R10 being as defined above.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the chelating monomer units of Formula 6 have the structure of Formula 20:
According to another particular embodiment, the present invention relates to the use as defined above, wherein the monomer units of Formula 7 have the structure of Formula 23, 24, 25 or
According to another particular embodiment, the present invention relates to the use as defined above, wherein the monomer units of Formula 7 have the structure of Formula 30, or 31, in particular the structure of Formula 32, or Formula 33:
According to another particular embodiment, the present invention relates to a use as defined above, wherein: the chelating monomer units of Formula 1 have the structure of Formula 8, 9, 10, 11, 12, 13, 14 or 15:
Formulas 8, 9, 13, 14, 15, 16, 17 and 18 wherein the —OH groups are in particular in a salified form, in particular in the —ONa form, and/or wherein the chelating monomer units of Formula 6 have the structure of Formula 19, 20 or 21:
Formulas 19, 21 and 22 wherein the —OH groups are in particular in a salified form, in particular in the —ONa form, and/or
Formulas 23, 24, 25, 26, 27, 28 and 29 wherein the OH groups are in particular in a salified form, in particular in the —ONa form.
According to another particular embodiment, the present invention relates to a use as defined above, wherein said monomer units are:
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of 100% of chelating monomer units of Formula 1.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of 100% of chelating monomer units of Formula 6.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of 100% of monomer units of Formula 7, Formula 7 wherein at least two of the R11 to R16 substituent represent a group other than a hydrogen atom.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1 and chelating monomer units of Formula 6.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1 and monomer units of Formula 7.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 6 and monomer units of Formula 7.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1, of chelating monomer units of Formula 6, and monomer units of Formula 7.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of:
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer comprises a structural unit of the Formula 39, or Formula 40:
According to this embodiment, the polymer, or the resin, is a homopolymer.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer comprises a structural unit of Formula 41, or of Formula 42:
According to this embodiment, the polymer, or the resin, is a copolymer comprising either a mixture of monomers of Formula 1 and of Formula 6, or a mixture of monomers of Formula 1 and of Formula 7, or a mixture of monomers of Formula 6 and Formula 7.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer comprises a structural unit of the Formula 43, or Formula 44:
According to this embodiment, the polymer, or the resin, is a copolymer comprising a mixture of monomers of Formula 1, Formula 6 and Formula 7.
According to another particular embodiment, the present invention relates to the use as defined above, wherein the polymer consists of:
A second object of the present invention is a method for preparing a crosslinked formaldehyde resin, said method comprising a step of heating a reaction medium comprising:
wherein:
at least one of the R1 to R5 substituents represents an —OH group or a salified form, and
at least one of the R1 to R5 substituents represents a hydrogen atom,
and wherein:
wherein:
wherein:
at least one of the R6 to R10 substituents represents an —OH group or a salified form, and
at least one of the substituents R6 to R10 substituents represents a hydrogen atom, and
wherein:
wherein:
at least one of the R11 to R16 substituents represents an —OH group or a salified form, and
at least two of the R11 to R16 substituents represent a hydrogen atom, and
wherein:
According to another particular embodiment, the present invention relates to a method of preparation as defined above, wherein the chelating monomer units are of Formula 1-A, said chelating monomer units of Formula 1-A possibly being mixed with at least one of the monomer units of Formulas 6-A and 7-A as defined above, said Formula 1-A being such that:
According to another particular embodiment, wherein the chelating monomer units are of Formula 1-A,
According to another particular embodiment, wherein the chelating monomer units are of Formula 6-A,
According to another particular embodiment, the present invention relates to a method of preparation as defined above, wherein the chelating monomer units are of Formula 6-A, said chelating monomer units of Formula 6-A possibly being mixed with at least one of the monomer units of Formulas 1-A and 7-A as defined above,
According to another particular embodiment, the present invention relates to a method of preparation as defined above, wherein the monomer units are of Formula 7-A, said monomer units of Formula 7-A being mixed with one at least monomer units of Formula 1-A and 6-A as defined above,
According to another particular embodiment, wherein the monomer units are of Formula 7-A, said monomer units of Formula 7-A being mixed with at least one of the monomer units of Formula 1-A and 6-A such as defined above,
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the base is a strong base, chosen in particular from lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide, in particular sodium hydroxide.
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the solvent is water.
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the aldehyde is chosen from formaldehyde, acetaldehyde, ethanal, n-propanal, isopropanal, n-butanal, isobutanal, n-pentanal, isopentanal, n-hexanal, isohexanal, n-heptanal, isoheptanal, n-octanal, isooctanal, n-nonanal, isononanal, n-decanal, isodecanal, benzaldehyde, terephthalaldehyde, isophthalaldehyde, glyoxal, furfural, succinaldehyde, glutaraldehyde, and trimesaldehyde.
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the aldehyde is formaldehyde or acetaldehyde.
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the aldehyde is formaldehyde, in particular in the form of formaldehyde, paraformaldehyde, or 1,3,5-tri oxane.
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein the heating step is carried out at a temperature of between 80° C. and 150° C.
“Temperature between 80° C. and 150° C.” also means the following ranges: from 80° C. to 140° C., from 80° C. to 130° C., from 80° C. to 120° C., from 80° C. ° C. to 110° C., from 80° C. to 100° C., from 80° C. to 90° C., from 90° C. to 150° C., from 100° C. to 150° C., from 110° C. to 150° C., 120° C. to 150° C., 130° C. to 150° C., 140° C. to 150° C., 90° C. to 140° C., and 100° C. to 120° C.
According to another particular embodiment, the present invention relates to a method of preparation as defined above, wherein the heating step is carried out for a time comprised from 16 to 96 hours, in particular approximately 24, 48, or 72 hours.
According to another particular embodiment, the present invention relates to a preparation method as defined above, further comprising, after the heating step, at least one washing step, said washing step being carried out in particular with:
According to another particular embodiment, the present invention relates to a preparation method as defined above, wherein:
According to another particular embodiment, the present invention relates to a method of preparation as defined above, further comprising, after the heating step, or after the washing step, a drying step, in particular in an oven at a temperature of 80° C., for 24 hours, to obtain a dried formo-phenolic resin.
According to another particular embodiment, the present invention relates to a method of preparation as defined above, further comprising, after the heating step, after the washing step, or after the drying step, a grinding step, to obtain a ground formo-phenolic resin.
According to another particular embodiment, the present invention relates to a preparation method as defined above, further comprising, after the heating step, at least one washing step, said washing step being carried out in particular with:
A third object of the present invention relates to a crosslinked formo-phenolic resin as obtained by the preparation method as defined above.
A fourth object of the present invention relates to a new crosslinked formo-phenolic resin, consisting of a polymer containing monomer units linked together by one or more —R11— group(s),
According to another particular embodiment, the present invention relates to a new formo-phenolic resin as defined above, wherein said resin consists of a polymer containing said monomer units bonded together by one or more —(CH2)-group(s).
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units are of Formula 1-B, wherein:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units are of Formula 1-B, wherein:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units are of Formula 6-B, wherein:
According to another particular embodiment, wherein the chelating monomer units are of Formula 6-B,
According to another particular embodiment, wherein the monomer units are of Formula 7-B, wherein:
According to another particular embodiment, wherein the monomer units are of Formula 7-B, wherein:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units of Formula 1-B have the structure of Formula 8-B
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units of Formula 1-B have the structure chosen from the structures of Formulas 10-B, of Formula 11-B, and of Formula 12-B:
According to another particular embodiment, wherein the chelating monomer units of Formula 6-B have the structure of Formula 19-B:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the chelating monomer units of Formula 6-B have the structure of Formula 20-B:
R8, R9 and R10 being as defined above, in particular the structure of Formula 22-B:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the monomer units of Formula 7-B have the structure of Formula 23-B, 24-B, 25-B or 26-B:
According to another particular embodiment, the present invention relates to a new formo-phenolic resin as defined above, wherein the chelating monomer units of Formula 1-B have the structure of Formula 8-B, 9-B, 10-B, 11-B, 12-B 13-B, 14-B or 15-B:
Formulas 8-B, 9-B, 13-B, 14-B, 15-B, 16-B, 17-B and 18-B wherein the —OH groups are in particular in a salified form, in particular in the form —ONa, and/or wherein the chelating monomer units of Formula 6 have the structure of Formula 19-B:
Formulas 19-B, 21-B and 22-B wherein the —OH groups are in particular in a salified form, in particular in the —ONa form, and/or wherein the monomer units of Formula 7 have the structure of Formula 23-B, 24-B, 25-B or 26-B:
Formulas 23-B, 24-B, 25-B, 26-B, 27-B, 28-B and 29-B n which the —OH groups are in particular in a salified form, in particular in the —ONa form.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the monomer units of Formula 7-B have the structure of Formula 30-B, or of Formula 31-B, in particular of structure of Formula 32-B, or of Formula 33-B:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer consists of 100% chelating monomer units of Formula 1-B.
According to another particular embodiment, the present invention relates to a new formo-phenolic resin as defined above, wherein the polymer consists of 100% of chelating monomer units of Formula 6-B.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1-B and monomer units Formula 6-B chelators.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1-B and monomer units of Formula 7-B.
According to another particular embodiment, the present invention relates to a new formo-phenolic resin as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 6-B and monomer units of Formula 7-B.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer consists of a mixture of chelating monomer units of Formula 1-B, monomer units chelators of Formula 6-B, and monomer units of Formula 7-B.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer consists of:
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer comprises a structural unit of Formula 39, or of Formula 40 as defined above.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer comprises a structural unit of Formula 41, or of Formula 42 as defined above.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the polymer comprises a structural unit of Formula 43, or of Formula 44 as defined above.
According to another particular embodiment, the present invention relates to a novel formo-phenolic resin as defined above, wherein the resin has a capacity for adsorption of uranium Qads greater than 5 mg/g, in particular greater than 10, 50, 10, 150, or 200 mg/g.
The adsorption capacity, noted Qads, expressed in mg of metal extracted per gram of resin, represents the quantity of this cation present in the resin, and which is determined by the following Formula 1:
According to another particular embodiment, the present invention relates to a formaldehyde resin as defined above, wherein the percentage of extraction of uranium E is greater than 10, in particular greater than 15, 20, 25, 30, 40, or 50.
The percentage of extraction, noted E and expressed in %, which represents the percentage of cation extracted by the resin compared to the initial quantity of cation, and which is determined by the following Formula 2:
According to another particular embodiment, the present invention relates to a formo-phenolic resin as defined above, wherein the distribution coefficient Ka is greater than 100 mL/g, in particular greater than 500 or 1000 mL/g.
The distribution coefficient, noted KD and expressed in mL/g, which represents the ratio between the quantity of this cation present in the resin and the quantity of this cation remaining in solution after extraction, and which is determined by the following Formula 3:
According to another particular embodiment, the present invention relates to a formo-phenolic resin as defined above, wherein the FSU/M separation factor is greater than 2, in particular greater than 5, 10, 50 or 100, in where U is uranium and M is the competing metal.
The separation factor, denoted FSU/M, represents the ratio between the KD of uranium and the KD of another metal, which makes it possible to quantify the selectivity of a resin to extract uranium with respect to another metal.
The separation factor is determined by the following Formula 4:
Among the competing metals M are other metals that may be present in an aqueous sample, in particular a sample of seawater.
Strontium, calcium, magnesium, sodium and kalium are examples of competing metals.
Said competing metals being present in a cationic form.
A fifth object of the present invention is a method for extracting uranium comprising: a step of bringing a formo-phenolic resin as defined above into contact with an aqueous solution comprising uranium, said solution aqueous being in particular sea water.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, further comprising, after the contacting step, a step for recovering the uranium, said recovery step being carried out in particular by eluting the resin with an alkaline aqueous solution.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, a step for regenerating the resin, in particular by washing the resin with:
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein the uranium is in an ionic form, in particular in the form of UO22+.
The present invention also relates to a method for extracting uranium, in particular in an ionic form, in particular in the form of UO22+, comprising: a step of bringing a formo-phenolic resin as defined above, with an aqueous solution comprising uranium, said aqueous solution being in particular sea water or river water.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, further comprising, after the contacting step, a step for recovering the uranium, said recovery step being carried out in particular by eluting the formo-phenolic resin with an alkaline aqueous solution, and optionally a step of regenerating the formo-phenolic resin, in particular by washing the formo-phenolic resin with:
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein the resin has a capacity for adsorption of uranium Qads greater than 5 mg/g, in particular greater than at 10, 50, 10, 150, or 200 mg/g.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein the percentage of extraction of uranium E is greater than 10, in particular greater than 15, 20, 25, 30, 40, or 50.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein the distribution coefficient Ka is greater than 100 mL/g, in particular greater than 500 or 1000 mL/g.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein the separation factor FSU/M is greater than 2, in particular greater than 5, 10, 50 or 100, where U is uranium and M is the competing metal.
According to another particular embodiment, the present invention relates to a method for extracting uranium as defined above, wherein:
The inventors have found, quite surprisingly, that the extraction method according to the present invention allows selective extraction of uranium, with a remarkable extraction percentage.
The resins have an unprecedented adsorption capacity.
The following examples illustrate the invention, without limiting its scope.
The chelating monomers of Formula 1 were obtained according to General Scheme 1:
To a solution of 2,3-dimethoxybenzoic acid (2.2 eq.) in anhydrous dichloromethane (0.8 M) was added dropwise oxalyl chloride (3 eq.) at room temperature.
A few drops of anhydrous 7V,7V-dimethylformamide were added and the medium was stirred for 2 h, until the end of the evolution of HCl. After evaporation of the solvents and residual oxalyl chloride, the residue was redissolved in anhydrous dichloromethane (0.8 M) and added dropwise to a solution of diamine (1 eq) and triethylamine (2.5 eq.) in anhydrous dichloromethane (0.8 M).
After 17 hours of stirring, the medium was washed twice with an aqueous solution of 1 M HCl, a saturated aqueous solution of NaCl, then dried over MgSO4 and evaporated under reduced pressure.
The residue obtained is purified by flash chromatography on silica gel using a cyclohexane/ethyl acetate gradient ranging from a ratio of 8/2 v/v to a ratio of 2/8 v/v in order to obtain a methylated bis-catecholamide in the form of a thick colorless oil with a yield of between 86% and 100%.
The following compounds were obtained:
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 8.02 (te, 1.5H), 7.96 (te, 0.5H), 7.60 (dd, J=7.9, 1.6 Hz, 1.5H), 7.57 (dd, J=8.0, 1.7 Hz, 0.5H), 7.12 (q, J=8.0 Hz, 2H), 7.04 (dd, J=8.1, 1.6 Hz, 2H), 3.87 (s, 6H), 3.86 (s, 6H), 3.39 (t, J=6.6 Hz, 1H), 3.30 (t, J=6.2 Hz, 3H), 1.90 (d, J=12.7 Hz, 1H), 1.83 (d, J=11.4 Hz, 2H), 1.70-1.53 (m, 3H), 1.41-1.25 (m, 2H), 1.03-0.84 (m, 2H);
RMN 13C (CD2Cl2, 100 MHz, 25° C.) δ (ppm): 165.11, 153.13, 147.87, 127.38, 124.52, 122.81, 115.52, 61.54, 56.35, 46.23, 43.97, 38.29, 35.67, 33.55, 33.15, 31.20, 29.82, 25.83, 21.07.
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 7.96 (se, 2H), 7.59 (d, J=7.9 Hz, 2H), 7.13 (t, J=7.9 Hz, 2H), 7.05 (d, J=7.9 Hz, 2H), 3.87 (s, 6H), 3.86 (s, 6H), 3.44 (q, J=6.4 Hz, 4H), 1.67 (quint, J=7.3 Hz, 4H), 1.54-1.45 (m, 2H);
RMN 13C (CD2C2, 100 MHz, 25° C.) δ (ppm): 165.12, 153.15, 147.90, 127.41, 124.54, 122.75, 115.51, 61.48, 56.36, 39.82, 29.76, 24.94.
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 8.33 (se, 2H), 7.64 (d, J=7.9 Hz, 2H), 7.35-7.27 (m, 4H), 7.14 (t, J=7.9 Hz, 2H), 7.07 (d, J=8.0 Hz, 2H), 4.63 (d, J=5.7 Hz, 4H), 3.87 (s, 6H), 3.81 (s, 6H);
RMN 13C (CD2Cl2, 100 MHz, 25° C.) δ (ppm): 165.26, 153.19, 148.08, 139.89, 129.24, 127.06, 126.88, 126.70, 124.59, 122.91, 115.82, 61.58, 56.40, 43.86.
To a solution of methylated bis-catecholamide synthesized in example IA (1 eq.) in anhydrous dichloromethane (0.08 M) was added dropwise BBr3 (7 eq.) with vigorous stirring at 0° C. The solution obtained (yellow or orange depending on the precursor) was stirred for 18 hours at room temperature then carefully added to crushed ice with vigorous stirring until the end of the hydrolysis.
The precipitate thus obtained was filtered, washed three times with ice water, and once with cold dichloromethane, then dissolved in methanol under reflux.
The solution was poured into water to precipitate the product.
The precipitate was filtered, washed three times with water and dried in order to obtain a phenolic monomer of Formula 1 in the form of a grey, beige or pink powder depending on the nature of the precursor with a yield of between 85% and 94%.
The following compounds were obtained:
RMN 1H (CD3OD, 400 MHz, 25° C.) δ (ppm): 7.20 (d, J=8.2 Hz, 2H), 6.92 (d, J=7.8 Hz, 2H), 6.68 (t, J=8.1 Hz, 2H), 4.86 (s, 6H), 3.21 (d, J=6.8 Hz, 4H), 1.87-1.76 (m, 3H), 1.66-1.53 (m, 3H), 1.33-1.21 (m, 2H), 0.90 (qd, J=12.8, 2.9 Hz, 2H);
RMN 13C(CD3OD, 100 MHz, 25° C.) δ (ppm): 171.42, 150.05, 147.26, 119.59, 119.52, 118.70, 116.92, 46.71, 44.40, 38.95, 36.29, 34.06, 31.84, 30.43, 26.49.
RMN 1H (CD3OD, 400 MHz, 25° C.) δ (ppm): 7.19 (dd, J=8.1, 1.1 Hz, 2H), 6.91 (dd, J=7.9, 1.1 Hz, 2H), 6.70 (t, J=8.0 Hz, 2H), 4.93 (s, 6H), 3.39 (t, J=7.1 Hz, 4H), 1.67 (quint, J=7.4 Hz, 4H), 1.50-1.42 (m, 2H);
RMN 1C(CD3OD, 100 MHz, 25° C.) δ (ppm): 171.47, 150.22, 147.30, 119.53, 118.59, 40.35, 30.08, 25.36.
RMN 1H (CD3OD, 400 MHz, 25° C.) δ (ppm): 7.35-7.21 (m, 6H), 6.92 (dd, J=7.9, 1.1 Hz, 2H), 6.70 (t, J=8.0 Hz, 2H), 4.93 (s, 6H), 4.56 (s, 4H);
RMN 13C(CD3OD, 100 MHz, 25° C.) δ (ppm): 171.46, 150.29, 147.31, 140.37, 129.76, 127.39, 127.31, 119.68, 119.63, 118.70, 116.68, 43.87.
The chelating monomers of Formula 6 were obtained according to General Scheme 2
To a solution of 2,6-dimethylanisole (1 eq.) in water (0.22 M) was added KMnO4 (2.1 eq.).
The solution was heated for 4 hours under reflux.
Another quantity of KMnO4 (2.1 eq.) was added and the reflux is maintained for an additional 2.5 hours.
The reaction medium was then left stirring for 17 hours at room temperature and then filtered through celite.
The precipitate was washed twice with hot water and the filtrate was concentrated under reduced pressure to one third of the initial volume.
The solution thus obtained was acidified to a pH of 2.5 by adding a concentrated solution of HCl. The precipitate thus obtained was filtered, washed with water and dried to obtain 2-methoxyisophthalic acid in the form of a white powder with a yield of 73%.
RMN 1H (DMSO-d6, 400 MHz, 25° C.) δ (ppm): 13.10 (s, 2H), 7.81 (d, J=7.7 Hz, 2H), 7.25 (t, J=7.7 Hz, 1H), 3.80 (s, 3H); RMN 13C (DMSO-d6, 100 MHz, 25° C.) δ (ppm): 167.03, 157.74, 133.50, 127.76, 123.60, 62.98.
To a solution of 2,3-dimethoxybenzoic acid (1.1 eq.) in anhydrous dichloromethane (0.4 M) was added oxalyl chloride (1.5 eq.).
After adding a few drops of N,N-dimethylformamide, the medium was stirred for 2 hours until the end of the release of HCl. After evaporation of the solvents and the residual oxalyl chloride, the residue was dissolved again in anhydrous dichloromethane (0.4 M) and added dropwise to a solution of N-Boc-ethylenediamine (1 eq.) and triethylamine (1.3 eq.) in anhydrous dichloromethane (0.4 M).
After 20 hours of stirring at room temperature, the medium was washed twice with an aqueous solution of 1 M HCl, a saturated solution of NaCl, then dried with MgSO4 and evaporated under reduced pressure.
The residue was purified by flash chromatography on silica gel with a gradient of dichloromethane/ethyl acetate from 10/0 to 4/6 in order to obtain the (2-(2,3-dimethoxybenzamido)ethyl)carbamate of tert-butyl in the form of a thick colorless oil with a yield of 93%.
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 8.17 (s, 1H), 7.60 (d, J=7.9 Hz, 1H), 7.14 (t, J=7.9 Hz, 1H), 7.06 (d, J=7.8 Hz, 1H), 5.02 (se, 1H), 3.89 (s, 3H), 3.88 (s, 3H), 3.53 (q, J=5.9 Hz, 2H), 3.32 (t, J=5.9 Hz, 2H), 1.40 (s, 9H);
RMN 13C (CD2C2, 100 MHz, 25° C.) δ (ppm): 166.00, 156.41, 153.18, 148.08, 126.98, 124.54, 122.74, 115.81, 79.36, 61.53, 56.39, 41.27, 40.07, 28.46.
To a solution of (2-(2,3-dimethoxybenzamido)ethyl)carbamate of tert-butyl (1 eq.), synthesized according to Example 2B, in dichloromethane (0.13 M) at 0° C. was added a solution of trifluoroacetic acid (20 eq.) in dichloromethane (3 M).
The solution thus obtained was stirred for 3 hours at room temperature then washed twice with an aqueous solution of NaOH until a pH>10 was obtained, a saturated solution of NaCl, water then evaporated under reduced pressure in order to obtain N-(2-aminoethyl)-2,3-dimethoxybenzamide in the form of an orange oil with a yield of 95%.
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 8.26 (se, 1H), 7.60 (d, J=7.8 Hz, 1H), 7.13 (t, J=8.0 Hz, 1H), 7.05 (d, J=7.9 Hz, 1H), 3.89 (s, 3H), 3.87 (s, 3H), 3.46 (q, J=5.9 Hz, 2H), 2.89 (t, J=5.9 Hz, 2H), 1.47 (s, 2H);
RMN 13C (CD2Cl2, 100 MHz, 25° C.) δ (ppm): 165.39, 153.21, 148.03, 124.49, 122.73, 115.57, 61.52, 56.37, 42.81, 41.96.
To a solution of 2-methoxyisophthalic acid, synthesized according to example 2A, (1 eq.) and hydrated HOBT (2.1 eq.) in THE (0.05 M) was added dropwise a solution of DCC (2.1 eq.) in THE (0.23 M) at 0° C. then the medium was stirred for four hours at room temperature.
The precipitate thus formed was filtered off and the filtrate was added dropwise to a solution of A-(2-aminoethyl)-2,3-dimethoxybenzamide (2.1 eq.) previously synthesized in THE (0.11 M) at 0° C. then the medium was stirred for twenty-four hours at room temperature.
Dichloromethane was then added to the reaction medium and the latter was washed twice with an aqueous solution of 1 M NaOH and water.
The organic phase was dried with MgSO4 and then concentrated under vacuum.
The residue was purified by flash chromatography on silica gel using a gradient of dichloromethane/methanol from 100/0 to 97/3 in order to obtain N1,N3-bis(2-(2,3-dimethoxybenzamido)ethyl)-2-methoxyisophthalamide in the form of a white powder with a yield of 97%.
RMN 1H (CD2Cl2, 400 MHz, 25° C.) δ (ppm): 8.28 (se, 2H), 8.00 (d, J=7.7 Hz, 2H), 7.77 (se, 2H), 7.59 (dd, J=7.9, 1.7 Hz, 2H), 7.26 (t, J=7.7 Hz, 1H), 7.13 (t, J=7.9 Hz, 2H), 7.06 (dd, J=8.2, 1.6 Hz, 2H), 3.86 (s, 6H), 3.85 (s, 6H), 3.76 (s, 3H), 3.71-3.67 (m, 8H);
RMN 13C (CD2Cl2, 100 MHz, 25° C.) δ (ppm): 166.13, 165.75, 156.59, 153.16, 148.08, 134.35, 128.49, 126.80, 125.09, 124.55, 122.65, 115.86, 63.78, 61.55, 56.36, 40.59, 39.84.
To a solution of N1,N3-bis(2-(2,3-dimethoxybenzamido)ethyl)-2-methoxyisophthalamide, synthesized according to Example 2D (1 eq.) in anhydrous dichloromethane (0.08 M) was added dropwise drop of BBr3 (9 eq.) with vigorous stirring at 0° C. The solution thus obtained was stirred for three days at room temperature and then carefully added to crushed ice with vigorous stirring until the end of the hydrolysis.
The precipitate thus obtained was filtered, washed three times with water and then dissolved in methanol under reflux.
The solution was added to water to precipitate the product.
The precipitate was filtered, washed three times with water and dried to obtain the phenolic monomer IPACAM, in the form of a beige powder with a yield of 95%.
RMN 1H (CD3OD, 400 MHz, 25° C.) δ (ppm): 7.96 (d, J=7.9 Hz, 2H), 7.18 (dd, J=8.0, 0.9 Hz, 2H), 6.96-6.90 (m, 3H), 6.69 (t, J=8.0 Hz, 2H), 4.94 (s, 9H), 3.63 (s, 8H);
RMN 13C(CD3OD, 100 MHz, 25° C.) δ (ppm): 172.08, 170.07, 161.40, 150.38, 147.31, 134.09, 119.69, 119.57, 119.26, 118.62, 116.54, 40.42, 40.17.
Formo-phenolic resins have been synthesized using:
A mixture of chelating monomer and phenolic monomer, or only chelating monomer, or only phenolic monomer was first dissolved in a NaOH solution with stirring.
Then, water is added in order to reach 100 equivalents with respect to the mixture of chelating monomer and phenolic monomer, or only to the chelating monomer, or only to the phenolic monomer.
The resulting solution was stirred and then the formaldehyde was added.
The reaction mixture was kept under stirring for 24 hours, after which it was transferred to a container with a wide neck and a flat bottom, such as a beaker, and then heated in a ventilated oven at 100° C. for 96 hours.
After solidification and then hardening of this mixture, the resin thus formed was recovered, ground using a ball mill and then washed.
Two types of successive washes were used depending on the form of resin to be obtained.
In all cases, the solutions used were added to the resin at a concentration of 40 mL/g of resin:
The resins thus washed were dried in a ventilated oven at 80° C. for 24 hours.
After drying, the resins were dispersed using a mortar and then dried again at 80° C. for 5 hours after which they were stored.
Twenty-six resins presented in Table 1 were thus synthesized.
The nature and the molar ratio of the various monomers used as well as the form wherein the resin was preserved after washing are also indicated.
The resins in Table 1 were characterized by elemental analysis.
By way of example, the elemental analysis results for the m-BENZCAM100-H, m-BENZCAM50-R50-H and m-BENZCAM34-R66-H resins are given below.
m-BENZCAM100-H:
Elemental analysis: C: 57.36%, H: 4.34%, N: 6.03%.
m-BENZCAM50-R50-H:
Elemental analysis: C: 56.79%, H: 4.39%, N: 4.56%.
m-BENZCAM34-R66-H:
Elemental analysis: C: 56.12%, H: 4.47%, N: 3.53%.
The ability of the resins to selectively extract uranium from seawater was determined by extraction tests carried out in discontinuous mode (batch), using, as aqueous solution, three different solutions, respectively referred to below solutions 1, 2 and 3, and consisting of:
avec:
Ci=initial concentration of the cation in solution (mg/L),
Cf=concentration of the cation in solution after extraction (mg/L),
V=volume of solution (mL),
m=mass of resin (mg).
Table 2 below presents the Qads, E and KD values obtained for uranium with twenty-four resins synthesized in example 3 and solutions 1 and 2 for Vim ratios equal to 1 and 4.
Table 3 below presents the values of Qads, E and KD obtained for uranium as well as the values of FSU/M (where M is a competing cation) obtained with the twenty-six resins synthesized in Example 3 and solution 3 for a V/m ratio equal to 1.
Table 4 These results show that formo-phenolic resins have a good affinity for uranium.
This affinity is greater when the resins contain a chelating monomer and even greater when they are in the deprotonated —ONa form.
In the presence of competing metals, the resins retain their good affinity for uranium.
In this case, the resins not only have a very good affinity for uranium, but also excellent selectivity with respect to all the competing metals tested.
For example, in the absence of competing metals, the m-BENZCAM34-R66-H resin makes it possible to extract almost half of its mass in uranium (Qads=446.2 mg/g).
This excellent affinity is preserved in the presence of competing metals (E=97%) with excellent selectivities.
In the presence of competing metals, the resin that seems to stand out from the others is 5-LICAM50-R50-Na with 100% uranium extraction, a uranium adsorption capacity of 49.2 mg/g and separation factors between 2548 and 37041.
This resin is indeed a striking example of the importance of adding a chelating phenolic monomer within the resin in order to increase the selectivity, since the RI 00-Na resin, containing only resorcinol, has separation only between 5 and 35.
These results, in terms of load capacity and selectivity, have never been achieved in the literature by other types of materials, for the extraction of uranium from seawater, by solid-liquid extraction.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010967 | Oct 2020 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/079703 | 10/26/2021 | WO |
