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    • 专利摘要:
    The present invention relates to a method for purifying a gaseous effluent containing at least one volatile organic compound (VOC), said process comprising at least the steps of: (a) disposing of at least one deep eutectic solvent (DES) comprising (aa) at least one compound of formula (I) R1R2R3R4Y + X-; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X-; and (b) contacting said deep eutectic solvent of step (a) with said gaseous effluent to be purified under conditions conducive to absorption of said VOC by said DES. The present invention further relates to the use of at least one deep eutectic solvent for absorbing at least one volatile organic compound contained in a gaseous effluent and a composition comprising at least one volatile organic compound and at least one deep eutectic solvent.
    公开号:FR3058905A1
    申请号:FR1661212
    申请日:2016-11-18
    公开日:2018-05-25
    发明作者:Sophie Fourmentin；David Landy；Leila Miriam Cunha Gomes De Moura；Sebastien Tilloy；Herve Bricout；Michel Ferreira
    申请人:Dartois, University of；Universite du Littoral Cote dOpale；
    IPC主号:
    专利说明:

    Holder (s): UNIVERSITE DU LITTORAL COTE DOPALE Public establishment, UNIVERSITE D'ARTOIS.
    Extension request (s)
    Agent (s): NONY CABINET.
    FR 3 058 905 - A1
    PROCESS FOR THE PURIFICATION OF A GASEOUS EFFLUENT.
    The present invention relates to a process for purifying a gaseous effluent containing at least one volatile organic compound (VOC), said process comprising at least the steps consisting in: (a) having at least one deep eutectic solvent ( DES) comprising (aa) at least one compound of formula (I) R! R 2 R 3 R4Y + X; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X; and (b) bringing said deep eutectic solvent of step (a) into contact with said gaseous effluent to be purified under conditions suitable for the absorption of said VOC by said DES. The present invention further relates to the use of at least one deep eutectic solvent for absorbing at least one volatile organic compound contained in a gaseous effluent as well as a composition comprising at least one volatile organic compound and at least one deep eutectic solvent.
    The present invention relates to a process for the purification of gaseous effluents containing volatile organic compounds (VOCs).
    90% of global VOCs emissions come from natural sources (biological fermentation, leakage of natural gas) and 10% from anthropogenic sources (from human activities).
    The impact of VOCs on the environment (water, soil, and air) and on certain individuals is not negligible.
    VOCs have harmful effects on humans in general because they can cause skin, eye, respiratory irritations, headaches, cardiac, digestive, renal, hepatic and central nervous system disorders. Some VOCs also have carcinogenic properties (benzene, formaldehyde) and others, such as toluene, are suspected of impairing reproductive functions.
    VOCs also play an important role in the troposphere, leading to an increase in the amount of ozone in the air, with its consequences on the environment and health.
    The processes for treating VOCs currently proposed are either recovering (absorption, adsorption and condensation) or destructive (thermal oxidation, catalytic oxidation, photocatalysis, and biological treatment).
    It is known that absorption methods are particularly advantageous, in particular in terms of efficiency (purification efficiency of the order of 90% to 98%), of range of concentration range of VOCs (effluents of concentration of from 2 to 50 g / Nm 3 at low or medium flow), and adaptability to many sectors of industrial activity (food industry, petrochemical industry, pharmacy, surface treatment, degreasing, painting, inks, adhesives, printing and packaging printing, textiles). In addition, absorption is a suitable solution for the recovery of products for which adsorption on activated carbon cannot be implemented (case of certain ketones reacting with activated carbon).
    Absorption corresponds to the washing of gas with a liquid solution during which the pollutants are transferred from the gas phase to the liquid phase. For obvious reasons, the affinity of the pollutant with the absorbent liquid phase is therefore decisive. The efficiency and the investment and operating costs are thus governed by the pollutant / absorbent couple.
    In addition, current washing methods by absorption are generally restricted to water-soluble VOCs insofar as they mainly use water or aqueous solutions using bases, acids or oxidizing reagents.
    With regard to the treatment of hydrophobic organic compounds (aromatic and aliphatic hydrocarbons for example), washing systems using heavy solvents, such as silicone oils, polyethylene glycol or adipates have been tested (Heymes et al., Chem. Eng. J., 2006, 115 (3), 225-231). However, their cost of use remains high and some of these compounds are not devoid of toxicity.
    More recently, studies have been carried out using ionic liquids (LI) as washing solvents (Quijano et al., Chem. Eng. Sc., 2011, 66 (12), 27072712, and Gonzalez-Miquel et al ., J. Phys. Chem. B, 2013, 117 (1), 296-306). However, although the LIs show a very good absorption capacity vis-à-vis the VOCs, they have, in addition to a certain toxicity, drawbacks linked to their synthesis (purification steps necessary). In fact, for example, LIs having BF 4 or PF 6 counterions are not stable and can release toxic by-products such as HF and POF 3 in the presence of moisture, which prevents any application of these compounds. (Freire et al., J. Phys. Chem. A 2010, 114, 3744-3749 and Swatloski et al., Green Chemistry, 2003, 5, 361-363).
    However, despite its many advantages, absorption remains little used due to the absence of versatile and low-cost washing solvents.
    There is therefore a very particular advantage of having a process for eliminating VOCs from gaseous effluents via absorption devoid of the aforementioned drawbacks.
    Thus, one of the objectives of the invention is to propose a process for the purification of gaseous effluents containing VOCs, making it possible to use inexpensive, non-toxic, available washing solvents, chemically inert and biodegradable.
    Another objective of the invention is to have a process for purifying gaseous effluents containing VOCs, using compounds which are effective as washing solvents with respect to both hydrophilic VOCs and Hydrophobic VOCs.
    Another objective of the invention is to provide a process for the purification of gaseous effluents containing VOCs, using easily recyclable washing solvents, without altering their absorption capacity during subsequent uses.
    Against all expectations, the inventors have found that the use of alternative solvents and more specifically deep eutectic solvents (DESs) makes it possible to meet this need.
    Thus, the present invention relates, according to a first aspect, to a process for purifying a gaseous effluent containing at least one volatile organic compound (VOC), said process comprising at least the steps consisting in:
    (a) have at least one deep eutectic solvent (DES) comprising:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X in which
    - Y is a nitrogen atom or a phosphorus atom;
    Ri, R 2 , R3 and R4 are independently of each other chosen from a hydrogen atom, a linear or branched C1-Cis alkyl, a linear or branched C1-C10 alkoxy, a C3-Cio cycloalkyl, a C 1 to C 10 aryl or a linear or branched C 7 to C 2 aralkyl, said alkyl, alkoxy, cycloalkyl, aryl and aralkyl possibly being substituted by one or more substituents chosen from a hydroxyl group, a halogen atom, a C 2 -C 10 acyl group, SR5 group, NH 2 group, CN group, NO 2 group, CO2R5 group, CHO group, COR5 group and OR5 group, where R5 is selected from an alkyl group C1 to C10 and a C3 to C10 cycloalkyl group; and
    - X is a halogen atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X '; and (b) bringing said deep eutectic solvent of step (a) into contact with said gaseous effluent to be purified under conditions suitable for the absorption of said VOC by said DES.
    Certainly DESs are already well known for their application in the absorption of gases such as carbon dioxide and sulfur dioxide (Yang et al., Green Chem., 2013, 15 (8), 2261-2265, Lin et al., J. Chem. Thermodynamics, 2014, 68, 216-220, Leron et al., J. Taiwan Inst. Chem. E., 2013, 44 (6), 879-885, and Zhang et al., Chem Soc Rev., 2012, 41 (21), 7108-7146), however, to the knowledge of the inventors, no study has so far focused on their use as washing solvents for VOCs.
    It is also known that DESs have physicochemical properties close to those of LI (density, viscosity, conductivity, surface tension, chemical inertia, etc.).
    However, unlike LI likely to be toxic depending on the nature of the cation or pennant, DESs are advantageously made up of "green" compounds and their preparation process does not require any purification step.
    Thus, DESs combine both the interesting physicochemical properties of LI with the advantage of being more environmentally friendly, and easier to implement.
    Consequently, DESs are an advantageous alternative to traditional washing solvents for several reasons, in terms of cost, availability, biodegradability, safety and effectiveness with respect to hydrophilic VOCs and hydrophobic VOCs.
    The method according to the invention may also comprise, following step (b), a step for recovering the purified gaseous effluent comprising a final concentration of VOCs of less than 110 mg.m ' 3 , and even better stripped ( free) of VOCs.
    Within the meaning of the invention, the expression “initial concentration of VOCs” designates the concentration of VOCs present in the gaseous effluent to be purified before purification, that is to say before the absorption of VOCs by DESs.
    For the purposes of the invention, the term "final concentration of VOCs" means the concentration of VOCs remaining in the purified gaseous effluent and which have therefore not been absorbed by the DESs.
    Thus, according to a particular embodiment, the method according to the invention further comprises, following step (b), the recovery of said gaseous effluent depleted in VOCs and preferably devoid (free) of VOCs.
    Within the meaning of the invention, the expression “depleted in VOCs” means that the final concentration of VOCs in the purified gaseous effluent is lower than the initial concentration of VOCs in the gaseous effluent intended to be purified.
    According to a particularly preferred embodiment, the final concentration of VOCs in the purified gaseous effluent can be zero. According to this embodiment, the recovered gaseous effluent is thus devoid (free) of VOCs.
    The invention relates, according to another aspect, the use of at least one deep eutectic solvent as defined in the present invention, for absorbing at least one volatile organic compound contained in a gaseous effluent.
    The invention relates, according to another aspect, to a composition comprising at least one volatile organic compound and at least one deep eutectic solvent as defined in the present invention.
    According to a particular embodiment, said volatile organic compound is present in the composition according to the invention in a form absorbed by said deep eutectic solvent as defined in the present invention.
    Advantageously, a composition according to the invention can also comprise at least one cyclodextrin.
    Indeed, the addition of cyclodextrin (s) to the compositions according to the invention makes it possible to improve the absorption capacity of DESs suitable for the invention, as shown in Example 5 below.
    Among the cyclodextrins which can be used in the compositions according to the invention, there may be mentioned in particular α-cyclodextrins, β-cyclodextrins (also called β-CD in the present description) and γ-cyclodextrins, substituted or unsubstituted.
    Among the substituted cyclodextrins, mention may more particularly be made of acyclodextrins, β-cyclodextrins and γ-cyclodextrins substituted by one or more methyl (s), hydroxypropyl (s) and / or sulfobutyl ether (s) groups.
    When they are substituted, the cyclodextrins suitable for the invention are preferably substituted β-cyclodextrins such as ΗΡ-β-CD (hydroxypropyl-βcyclodextrins), SBE ^ -CD (sulfobutylether ^ -cyclodextrins) and β- methylated cyclodextrins such as DIMEB (heptakis (2,6-di-O-methyl) ^ - cyclodextrin), RAMEB (β-cyclodextrin statistically methylated or randomly-methylated ^ -cyclodextrin, in English), TRIMEB (heptakis (2 , 3,6-tri-O-methyl) ^ - cyclodextrin) and CRYSMEB (weakly methylated βcyclodextrin).
    Thus, according to a particularly preferred embodiment, the compositions according to the invention can also comprise at least one cyclodextrin chosen from α-cyclodextrins, β-cyclodextrins, γ-cyclodextrins, substituted or not, and their mixtures, of preferably chosen from a β-cyclodextrin, RAMEB, and mixtures thereof, and even more preferably chosen from a β-cyclodextrin and RAMEB.
    As appears from the experimental part which follows, the method according to the invention is particularly advantageous and this in more ways than one.
    More specifically, it allows access to an absorption capacity of between 70% and 100% of the initial amount of hydrophilic or hydrophobic VOCs.
    In addition, the inventors have discovered that the Henry's constant (H cc ) of VOCs, a determining thermodynamic quantity in absorption processes, is significantly much lower than that of the same compound in water, which translates into better absorbent capacity.
    The inventors have also shown that for example, for toluene, the Henry constants determined for DESs based on tetrabutylphosphonium bromide (TBP) and tetrabutylammonium bromide (N 444 4Br) are of the same order of magnitude as those obtained in ionic liquids and silicone oils.
    The inventors have also found that the presence of moisture in the gaseous effluents does not cause any harmful effect (s) in the absorption process according to the invention.
    Finally, the inventors have demonstrated that the recycling of the absorbent solution comprising DESs suitable for the invention has no negative impact on its absorption capacity.
    PROCESS ACCORDING TO THE INVENTION
    Definition of deep eutectic solvents (DESs)
    Deep eutectic solvents are alternative solvents (or "green solvents") which were discovered in 2003 by Abbott et al. (Chem. Commun., 2003, 9, 7071). They are generally composed of two or three constituents which are capable of self-association, often by hydrogen bonds, to form a eutectic mixture having a melting point lower than that of each constituent taken individually.
    More particularly, the DESs in accordance with the invention consist of a mixture of a hydrogen bond acceptor compound (also called HBA) represented by an ammonium or phosphonium salt and of a hydrogen bond donor compound (also called HBD).
    More particularly, a deep DES suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X 'in which
    - Y is a nitrogen atom or a phosphorus atom;
    Ri, R 2 , R3 and R4 are independently of each other chosen from a hydrogen atom, a linear or branched C1-Cis alkyl, a linear or branched C1-C10 alkoxy, a C3-Cio cycloalkyl, a C 1 to C 10 aryl or a linear or branched C 7 to C 2 aralkyl, said alkyl, alkoxy, cycloalkyl, aryl and aralkyl possibly being substituted by one or more substituents chosen from a hydroxyl group, a halogen atom, a C 2 -C 10 acyl group, SR5 group, NH 2 group, CN group, NO 2 group, CO2R5 group, CHO group, COR5 group and OR5 group, where R5 is selected from an alkyl group C1 to C10 and a C3 to C10 cycloalkyl group; and
    - X is a halogen atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X '.
    In the context of the present invention:
    - The compound of formula (I) is a hydrogen bond acceptor and the compound (II) is a hydrogen bond donor.
    - C1-Cis alkyl denotes an alkyl group comprising from 1 to 18 carbon atoms. Such an alkyl group may be linear or branched and may be chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.
    By analogy, a C1-C4 alkyl denotes an alkyl group comprising from 1 to 4 carbon atoms.
    a C1 to C10 alkoxy denotes an alkoxy group comprising from 1 to 10 carbon atoms. Such an alkoxy group can be linear or branched and can be chosen from methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, nonoxy, decoxy.
    a C3 to C10 cycloalkyl denotes a cycloalkyl group comprising from 3 to 10 carbon atoms. Such a cycloalkyl group can be chosen from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
    - G, C10 aryl denotes a monocyclic or bicyclic aryl group comprising from 6 to 10 carbon atoms. Such an aryl group can be chosen from phenyl or naphthyl.
    a C7 to C12 aralkyl denotes a group comprising an alkyl part and an aryl part, all of these two parts comprising from 7 to 12 carbon atoms and the alkyl part being linked to the radical Y represented by the phosphorus atom or the nitrogen atom. The aryl part can be monocyclic or bicyclic and the alkyl part can be linear or branched. Such an aryl group can be chosen from benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthylmethyl, naphthylethyl.
    - A C 2 to C 10 acyl denotes an acyl group comprising 2 to 10 carbon atoms. Such an acyl group can be linear or branched and can be chosen from acetyl, propionyl, butyryl, pentanoyl, hexanoyl (or caproyl), heptanoyl, octanoyl, nonanoyl.
    As stated above, the alkyl, alkoxy, cycloalkyl, aryl and aralkyl groups may, independently of one another, be substituted by one or more substituents chosen from a hydroxyl group, a halogen atom, a C 2 to C 10 acyl group, an SR5 group, an NH 2 group, a CN group, an NO 2 group, a CO2R5 group, a CHO group, a COR5 group and an OR5 group, where R5 is chosen from a C1-C6 alkyl group or a cycloalkyl group in C3 to Cio.
    According to a particular embodiment, the radical X of the compound of formula (I) is a chlorine, bromine, fluorine or iodine atom, preferably a chlorine or bromine atom.
    According to another particular embodiment, the groups Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl optionally substituted by one or more substituents chosen from a hydroxyl group, an atom halogen, C 2 -C 10 acyl group, SR5 group, NH 2 group, CN group, NO 2 group, CO2R5 group, CHO group, COR5 group and OR5 group, where R5 is selected from a C1-Cis alkyl group and a C3-C10 cycloalkyl group, preferably a hydroxyl group.
    According to a preferred embodiment, the groups Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl optionally substituted by one or more hydroxyl groups, preferably chosen from a alkyl Ci to C4 linear optionally substituted by one or more hydroxyl groups.
    According to a preferred embodiment, the groups Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl optionally substituted by a hydroxyl group, preferably from a C1-C4 alkyl linear optionally substituted by a hydroxyl group.
    According to a preferred embodiment, the compound of formula (I) is chosen from choline chloride (also abbreviated ChCl in the present description), tetrabutylphosphonium bromide (also abbreviated TBP in the present description), tetrabutylammonium bromide ( also abbreviated N4444Br in the present description), and their mixtures.
    According to a particular embodiment, the compound (II) is chosen from levulinic acid (also abbreviated Lev in the present description), urea (also abbreviated U in the present description), ethylene glycol (also abbreviated as EG in the present description), glycerol (also abbreviated G in the present description), decanoic acid (also abbreviated Dec in the present description), an alkylene glycol, malonic acid, thiourea, N-methylurea, Ν , Ν'-dimethylurea, N, N-dimethylurea, acetamide, benzamide, 2,2,2-trifluoroacetamide, imidazole, adipic acid, benzoic acid, benzyl alcohol, acid citric, phenol, // - methylphenol, o-methylphenol, m-methylphenol, // - chlorophenol, D-fructose, vanillin, oxalic acid, oxalic acid dihydrate, aniline , phenyl acetic acid, 3-phenylpropionic acid, succinic acid, tricarballylic acid, itaconic acid, xylitol, D-sorbitol, L - (+) - tartaric acid, D-isosorbide, 4-hydroxybenzoic acid, caffeic acid, acid // coumaric, trans-cinnamic acid, octanedioic acid, gallic acid, resorcinol, and their mixtures, preferably chosen from levulinic acid, urea, ethylene glycol, glycerol, decanoic acid, and mixtures thereof.
    According to a particular embodiment, a deep DES suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R 3 R4Y + X 'ίο in which
    - Y is a nitrogen atom or a phosphorus atom;
    - Ri, R2, R3 and R4 are independently of each other chosen from a hydrogen atom, a linear or branched C1-Cis alkyl, a linear or branched C1-C10 alkoxy, a C3-Cio cycloalkyl, a Cù to C10 aryl or linear or branched C7 to C12 aralkyl, said alkyl, alkoxy, cycloalkyl, aryl and aralkyl may be substituted by one or more substituents chosen from a hydroxyl group, a halogen atom, an acyl group in C2 to Cio, an SR5 group, an NH 2 group, a CN group, a NO2 group, a CO2R5 group, a CHO group, a COR5 group and an OR5 group, where R5 is chosen from a C1 to C6 alkyl group and a C3 to C10 cycloalkyl group; and
    - X is a halogen atom; and (bb) at least one compound (II) which is a hydrogen bonding donor capable of forming a complex with X 'chosen from levulinic acid, urea, ethylene glycol, glycerol, decanoic acid, an alkylene glycol, malonic acid, thiourea, Nmethylurea, N, N'-dimethylurea, Ν, Ν-dimethylurea, acetamide, benzamide, 2,2,2tnfluoroacetamide, imidazole, adipic acid , benzoic acid, benzylic alcohol, citric acid, phenol, // - methylphenol, o-methylphenol, m-methylphenol, / - chlorophenol, D-fructose, vanillin, oxalic acid, oxalic acid dihydrate, aniline, phenylacetic acid, 3-phenylpropionic acid, succinic acid, tricarballylic acid, itaconic acid, xylitol, D-sorbitol, L - (+) - tartaric acid, Disosorbide, 4-hydroxybenzoic acid, caffeic acid, // - coumaric acid, trans-cinnamic acid, octanedioic acid, gallic acid, resorcinol, and mixtures thereof, preferably selected from levulinic acid, urea, ethylene glycol, glycerol, decanoic acid, and mixtures thereof.
    According to a particular embodiment, a deep DES suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X in which
    - Y is a nitrogen atom or a phosphorus atom;
    - Ri, R2, R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl, said alkyls being able to be substituted independently of each other by at least one hydroxyl group;
    and (bb) at least one compound (II) which is a hydrogen bonding donor capable of forming a complex with X 'chosen from levulinic acid, urea, ethylene glycol, glycerol, and decanoic acid .
    According to a particular embodiment, a DES suitable for the invention is chosen from choline chloride: urea, choline chloride: glycerol, choline chloride: ethylene glycol, choline chloride: levulinic acid, bromide tetrabutylphosphonium glycerol, tetrabutylphosphonium bromide: levulinic acid, tetrabutylphosphonium bromide: ethylene glycol, tetrabutylammonium bromide: decanoic acid, and mixtures thereof, preferably chosen from choline chloride: urea, choline chloride: glycerol, choline chloride: ethylene glycol, choline chloride: levulinic acid, tetrabutylphosphonium bromide: glycerol, tetrabutylphosphonium bromide: levulinic acid, tetrabutylphosphonium bromide: ethylene glycol, and tetrabutylammonium bromide: decanoic acid.
    According to a particularly preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X in which
    - Y is a nitrogen atom;
    - Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1 to C18 alkyl, said alkyls being able to be substituted independently of each other by at least one hydroxyl group; and
    - X is a chlorine atom or a bromine atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X 'chosen from levulinic acid, decanoic acid, urea, glycerol and ethylene glycol.
    According to another particularly preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X in which
    - Y is a phosphorus atom;
    - Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl; and
    - X is a bromine atom; and (bb) at least one compound (II) which is a hydrogen bonding donor capable of forming a complex with X'choisi among levulinic acid, ethylene glycol and glycerol.
    According to an even more preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R 3 R4Y + X 'in which
    - Y is a nitrogen atom;
    - Ri, R 2 , R3 and R4 are independently of each other chosen from a linear C1-C4 alkyl, said alkyls being able to be substituted independently of each other by at least one hydroxyl group; and
    - X is a chlorine atom or a bromine atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X 'chosen from levulinic acid, decanoic acid, urea, glycerol and ethylene glycol.
    According to another even more preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R 3 R4Y + X 'in which
    - Y is a nitrogen atom;
    - Ri, R 2, R 3 and R 4 are independently from each other selected from alkyl to C 4 linear alkyl lesdit may be substituted independently of each other by at least one hydroxyl group; and
    - X is a chlorine atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X'choisi among levulinic acid, urea, glycerol and ethylene glycol.
    According to another even more preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) R 1 R 2 R 3 R 4 Y + X 'in which
    - Y is a nitrogen atom;
    - Ri, R 2, R 3 and R are independently from each other selected from alkyl to C 4 linear; and
    - X is a bromine atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X 'represented by decanoic acid.
    According to another even more preferred embodiment, a deep eutectic solvent suitable for the invention comprises:
    (aa) at least one compound of formula (I) RiR 2 R 3 RiY + X 'in which
    - Y is a phosphorus atom;
    - Ri, R 2, R 3 and R are independently from each other selected from alkyl to C 4 linear; and
    - X is a bromine atom;
    and (bb) at least one compound (II) which is a hydrogen bonding donor capable of forming a complex with X'choisi among levulinic acid, ethylene glycol and glycerol.
    According to a particular embodiment, the molar ratio of compound (I) to compound (II) ranges from 1: 1 to 1: 12, in particular is 1: 1, 1: 2, 1: 3, 1: 4, 1: 5, 1: 6, 1: 7, 1: 8, 1: 9, 1:10, 1:11 or 1:12, and preferably from 1: 1 to 1: 6.
    A DES suitable for the invention is a liquid having a viscosity of less than 5,000 mPa.s, preferably ranging from 10 mPa.s to 1,000 mPa.s measured at 30 ° C.
    The viscosity of the DESs suitable for the invention is for example measured using a Stabinger Viscometer ™: SVM 3000 (Anton-Paar) at a temperature of 30 ° C.
    In addition, a DES suitable for the invention has a melting temperature (Tf) or a glass transition temperature (T g ) of less than 80 ° C, preferably between -66 ° C and 25 ° C.
    As explained above, the DESs suitable for the invention are not chemically reactive with the absorbed VOCs. This characteristic is advantageous to allow easy implementation of the method according to the invention.
    The DESs according to the invention can be prepared in any manner known to those skilled in the art. As mentioned above, advantageously, their synthesis process does not require any purification step.
    For example, the DESs suitable for the invention can be synthesized according to the following protocol.
    Compounds (I) and (II) are mixed in a molar ratio ranging from 1: 1 to 1: 12, preferably from 1: 1 to 1: 6. The mixture is then subjected to stirring at atmospheric pressure and at a temperature below 100 ° C (preferably 60 ° C, at P a t m for 24 h) until a homogeneous liquid is obtained. The solvents obtained are then characterized by measuring their melting point.
    Definition of volatile organic compounds (VOCs)
    “Volatile organic compound” means any chemical compound having carbon and hydrogen, which can be replaced by other atoms such as halogens, oxygen, phosphorus or sulfur and having a vapor pressure saturating greater than 10 Pa under normal conditions of temperature and pressure having a corresponding volatility under particular conditions of use (pressure and temperature).
    As mentioned above, advantageously, the hydrophilic VOCs and the hydrophobic VOCs can be absorbed by the DESs used according to the present invention.
    Thus, among the volatile organic compounds suitable for the invention, there may be mentioned in particular:
    - alkanes, in particular ethane, propane, pentane, butane, isopentane, hexane, and fert-butylcyclohexane;
    - alkenes, in particular ethylene, propylene, 1-decene, and limonene;
    - arenas, in particular benzene, toluene, xylene, ethylbenzene, styrene, and anethole;
    - aldehydes, in particular formaldehyde, and acetaldehyde;
    - ketones, in particular methyl ethyl ketone (also abbreviated MEK in the present description) and methyl isobutyl ketone;
    - esters, in particular methyl acetate, ethyl acetate, propyl acetate, and butyl acetate;
    - chlorinated volatile organic compounds, in particular dichloromethane, trichloromethane, tetrachloromethane, trichlorethylene, tetrachlorethylene and vinyl chloride;
    - volatile organic sulfur compounds, in particular mercaptans and alkylsulfides, more particularly dimethylsulfide, dimethyldisulfide, and diethyl sulfide;
    - and their mixtures.
    More particularly, a VOC suitable for the invention is chosen from toluene, dichloromethane, acetaldehyde, methyl ethyl ketone, tert-butyl cyclohexane, 1-decene, limonene, anethol and their mixtures, even more preferably from toluene , dichloromethane, acetaldehyde, methyl ethyl ketone, fert-butylcyclohexane, 1-decene, limonene, and anethole.
    The initial concentration (i.e. before purification of the gaseous effluent) of VOC (s) is between 1 g.m ' 3 and 10,000 g.m' 3 , preferably between 2.9 g.m ' 3 and 1180 gm ' 3 .
    The values of the Henry's constants (H cc ) of the VOCs in the DESs suitable for the invention are determined by the ratio of the concentrations in the gas phase and in the liquid phase (H cc = C ga z / Ciiq). An adaptation of the VPC method (Vapor Phase Calibration method, in English, or vapor phase calibration method) has thus been developed so that it can be applied to DESs. Vials containing VOC in aqueous solution are used as a reference. From the dimensionless Henry's constant determined in solution and from the law of mass conservation, the inventors were able to calculate the concentration of VOCs in the head space of the flasks containing the aqueous solutions. This allowed them to obtain a calibration connecting the area of the chromatographic peak with the concentration of VOC in the headspace (gas phase). The Henry's constant of VOCs in DES is then obtained by the law of mass conservation from this calibration line by making the relationship between the concentration of VOC in the gas phase and the concentration of VOC in DES (C ga z / Ciiq). The H cc are between 0.0001 and 0.3000, preferably between 0.0001 and 0.2300.
    VOC / DES couples
    From the experimental part, and more precisely from Table 3 of Example 2, it appears that certain VOC pollutants have more affinity than others with respect to a given absorbent.
    Thus, according to a preferred embodiment, a pollutant / absorbent couple (VOC / DES) according to the invention is chosen from:
    - toluene / TBP: Lev;
    - toluene / N4444Br: Dec;
    - toluene / TBP: G;
    - toluene / ChCl: Lev;
    - dichloromethane / TBP: Lev;
    - dichloromethane / N4444Br: Dec;
    - dichloromethane / TBP: G;
    - acetaldehyde / TBP: G;
    - acetaldehyde / ChCl: U;
    - acetaldehyde / ChCl: G;
    - methyl ethyl ketone / TBP: EG;
    - / "/ 7-butylcyclohexane / TBP: EG;
    - 1-decene / TBP: EG;
    - Anethole / ChCl: U;
    - Anethole / ChCl: EG;
    - Anethole / ChCl: G;
    - Anethole / ChCl: Lev;
    - Limonene / ChCl: Lev; and
    - Limonene / TBP: EG.
    According to a more preferred embodiment, this polluting / absorbing couple (VOC / DES) is chosen from:
    - toluene / TBP: Lev;
    - toluene / N4444Br: Dec;
    - dichloromethane / TBP: Lev;
    - dichloromethane / N4444Br: Dec;
    - acetaldehyde / TBP: G;
    - / "/ 7-butylcyclohexane / TBP: EG,
    - 1-decene / TBP: EG,
    - Anethole / ChCl: U;
    - Anethole / ChCl: EG;
    - Anethole / ChCl: G;
    - Anethole / ChCl: Lev; and
    - Limonene / TBP: EG.
    The COVs / DESs weight ratio is between 0.0003 and 0.08 at 30 ° C.
    Reaction conditions
    As explained above, the method according to the invention comprises a step (a) of making available at least one deep eutectic solvent and a step (b) of bringing said DES into contact with the gaseous effluent to be purified under conditions conducive to the absorption of said VOC by said DES.
    The purification process according to the invention is carried out at a temperature between 20 ° C and 100 ° C, preferably between 30 ° C and 60 ° C.
    According to the invention, the absorption of the VOC (s) is carried out by bringing the gaseous effluent to be purified into contact with the DES (s) suitable for the invention by any means known to man. art to achieve gas / liquid contact.
    The gaseous effluent to be purified can have a flow rate of between 100 m 3 / h and 100,000 m 3 / h, preferably between between 100 m 3 / h and 10,000 m 3 / h and, as explained above, a concentration of VOCs between 1 gm ' 3 and 10,000 g.m' 3 , preferably between 2.9 g.m ' 3 and 1180 g.m' 3 .
    Thus, this contacting can be obtained in a transfer unit by bubbling gas through the DES, by passing the co-current or counter-current of the gaseous effluent and the DES through a packed column, or by passing the the gaseous effluent in a column in which the DES is sprayed by any means such as mechanical, pneumatic, electrostatic.
    It is also possible to carry out this contacting by suction of the gaseous effluent to be purified in a venturi, the liquid fluid of which is the absorption solvent, or an injector device.
    The purified effluent is then recycled, released into the atmosphere or fed into another process such as another purification process.
    In fact, in addition to VOCs, other compounds such as inorganic gases (CO2, NOx, etc.) can be contained in the gaseous effluents intended to be purified using the method according to the invention.
    Of course, the presence of these other constituents in the gaseous effluents must not be such as to disturb / alter the efficiency of the absorption of VOCs by the DESs via the process according to the invention.
    Thus, when these compounds, which are different from the VOCs, are considered to be toxic / pollutants, the effluent purified according to the method of the invention can subsequently be subjected to at least one other purification method, different from the method according to invention, in order to eliminate these undesirable compounds.
    On the contrary, if these compounds, distinct from VOCs, have a certain harmlessness, the effluent purified according to the process of the invention can be released directly into the atmosphere.
    The method according to the invention can be implemented by circulation, preferably in a closed loop.
    Thus, in a preferred embodiment, the DES solution generally flows in a closed loop.
    The process can be implemented in continuous, semi-continuous or batch mode.
    In an advantageous embodiment, the method according to the invention is implemented in batch.
    The DES absorbent solution suitable for the invention can then be recycled for later reuse. This solution can be used and recycled several times.
    Advantageously, as demonstrated in the experimental part, recycling after each use has no negative impact on the absorbent capacity of the DES concerned.
    The elimination of the VOC (s) absorbed in the DES solution is carried out by heating the composition according to the invention, for example in an oven, at a temperature between 30 ° C. and 80 ° C., preferably between 40 ° C and 60 ° C, in particular at 60 ° C for a period of between 24 and 72 hours, preferably between 24 and 48 hours, in particular 2 days.
    The purification efficiency of the gaseous effluent obtained with the process according to the invention is between 45% and 100%, preferably between 70% and 100%, more preferably between 95% and 100%.
    In general, the method according to the invention can be applied industrially for the treatment of emissions of gaseous discharges loaded with VOCs at the outlet of the stack by absorption.
    The expressions "between ... and ..." and "ranging from ... to ..." must be understood including limits, unless otherwise specified.
    The examples and figures which follow will allow a better understanding of the invention, without however being limiting in nature.
    FIGURES
    - Figure 1 illustrates a diagram of the study of the absorption of VOCs by DESs in static mode.
    - Figure 2 illustrates three consecutive tests of toluene absorption by the same solution of DES ChCl: U at an initial VOC concentration of 59 g.m ' 3 at 30 ° C, the second and third tests each being carried out after recycling the solution recovered from the previous test by heating at 60 ° C for 2 days.
    - Figure 3 shows an arrangement developed for the absorption of VOCs by DESs in dynamic mode.
    - Figure 4 illustrates the solubility (mg.g ' 1 ) of toluene in “pure” ChCl: U (cyclodextrin concentration of 0% by weight) and in ChCl: U solutions with β-CD or RAMEB cyclodextrins with an initial VOC concentration of 59 gm 3 and a cyclodextrin concentration of 2%, 4%, 8% and 10% by weight at 30 ° C.
    - Figure 5 illustrates the solubility (mg.g ' 1 ) of toluene in pure DESs (ChCl: U; ChCl: G; TBP: G and TBP: EG) and solutions of DESs (ChCl: U; ChCl: G ; TBP: G and TBP: EG) with water with an initial VOC concentration of 59 gm ' 3 and a water concentration of 0.5% and 5% by volume, at 30 ° C.
    EXAMPLES
    As explained above, the following abbreviations are used:
    ChCl for Choline Chloride
    TBP for Tetrabutylphosphonium Bromide
    N 44 44Br for Tetrabutylammonium bromide
    U for Urea
    Lev for Levulinic Acid
    G for Glycerol
    EG for Ethylene glycol
    Dec for Decanoic acid
    MEK for methyl ethyl ketone
    RAMEB for statistically methylated β-cyclodextrin β-CD for β-cyclodextrin
    EXAMPLE 1 Preparation of DESs suitable for the invention
    Compounds (I) and (II) are mixed in a molar ratio of between 1: 1 and 1: 6. The quantity of each partner depends on the desired final quantity. The mixture is then subjected to stirring at atmospheric pressure and at a temperature below 100 ° C (preferably 60 ° C, at P a tm for 24 h) until a homogeneous liquid is obtained. The solvents obtained are then characterized by measuring their melting point (see Table 1 below).
    1.1 Choline chloride: Urea (molar ratio 1: 2)
    60.06 g of urea are added to 69.82 g of choline chloride and stirred at 60 ° C until a homogeneous solution is obtained.
    1.2 Tetrabutylphosphonium bromide: Glycerol (1: 1 molar ratio)
    169.67 g of tetrabutylphosphonium bromide are added to 46.04 g of glycerol and stirred at 60 ° C until a homogeneous solution is obtained.
    1.3 Tetrabutylammonium bromide: Decanoic acid (molar ratio 1: 2)
    161.184 g of tetrabutylammonium bromide are added to 172.26 g of decanoic acid and stirred at 60 ° C until a homogeneous solution is obtained.
    1.4 Tetrabutylphosphonium bromide: Levulinic acid (molar ratio
    1: 6)
    169.67 g of tetrabutylphosphonium bromide are added to 348.33 g of levulinic acid and stirred at 60 ° C until a homogeneous solution is obtained.
    1.5 Choline chloride: Glycerol (molar ratio 1: 2)
    69.82 g of choline chloride are added to 92.09 g of glycerol and stirred at 60 ° C until a homogeneous solution is obtained.
    1.6 Choline chloride: Ethylene glycol (molar ratio 1: 2)
    69.82 g of choline chloride are added to 62.07 g of ethylene glycol and stirred at 60 ° C until a homogeneous solution is obtained.
    1.7 Choline chloride: Levulinic acid (molar ratio 1: 2)
    69.82 g of choline chloride are added to 116.11 g of levulinic acid and stirred at 60 ° C until a homogeneous solution is obtained.
    1.8 Tetrabutylphosphonium bromide: Ethylene glycol (molar ratio 1: 2) 15 169.67 g of tetrabutylphosphonium bromide are added to 62.07 g of ethylene glycol and stirred at 60 ° C until a homogeneous solution is obtained.
    Table 1 below summarizes the DESs suitable for the invention which are prepared according to the synthesis protocols described above, as well as their corresponding melting temperature (Tf) or glass transition temperature (T g ).
    Table 1
    OF(HBA: HBD) HBA: HBDmolar T f / Tg (in ° C) ChCl: U 1: 2 12 ChCl: G 1: 2 -33 ChCbEG 1: 2 -66 ChCbLev 1: 2 Liquid at room temperature (20 ° C) TBP: G 1: 1 Liquid at room temperature (20 ° C) TBP: Lev 1: 6 Liquid at room temperature (20 ° C) TBP: EG 1: 2 Liquid at room temperature (20 ° C) N 4 44 4 Br: Dec 1: 2 Liquid at room temperature (20 ° C)
    EXAMPLE 2: Evaluation of the potential for trapping VOCs in the DESs suitable for the invention
    The potential for trapping VOCs in DESs is determined by gas chromatography coupled to the headspace.
    More particularly, the affinity of three VOCs, namely toluene, dichloromethane and acetaldehyde, is established with respect to the DESs illustrated in table 1 above.
    Materials and methods
    For the determination of the solubility of VOCs in DES, solutions of VOCs in ethanol at a concentration of 10,000 ppm and 100,000 ppm are first prepared. Volumes between 10 µL and 200 µL of these solutions are added to 3 mL of DES in a vial which is then sealed. The bottle is kept for 24 hours with magnetic stirring at room temperature (or under slight heating if the DES is too viscous at room temperature 20 ° C).
    After 24 hours with stirring, the flask containing the DES and the VOC is placed in the head space and the gas phase is analyzed by gas chromatography. The area of the resulting VOC peak is compared with the area of the peaks obtained by calibration and the concentration and amount of VOC in the gas phase of each bottle is calculated. Thus the amount of VOC in the head space of the bottle is established in relation to the calibration of VOC in water. Knowing the total amount of VOC added to the bottle and the amount present in the gas phase, the amount retained by the liquid phase (DES) is obtained by difference between these two values.
    The values of the Henry's constants of the VOCs in the DESs are also determined by the ratio of the concentrations in the gas phase and in the liquid phase (H cc = C ga z / Ciiq). The Henry's constant (H cc ) is the determining thermodynamic quantity in the absorption processes. It must be as low as possible to obtain better absorbency.
    As explained above, an adaptation of the VPC method has been developed so that it can be applied to DESs. Vials containing VOC in aqueous solution are used as a reference. From the Henry dimensionless constant determined in solution and from the law of mass conservation, the inventors were able to calculate the VOC concentration in the head space of the bottles containing the aqueous solutions. This allowed them to obtain a calibration linking the area of the chromatographic peak with the concentration of VOC in the headspace (gas phase). Henry's constant of VOCs in DESs is then obtained by the law of mass conservation from this calibration line by making the relationship between the concentration of VOC in the gas phase and the concentration of VOC in DES (Cgaz / Ciiq).
    A decrease in the Henry's constant of VOCs up to 200 times compared to the Henry's constant of the compound in water is shown. Table 2 below groups together the values of the Henry's constants of eight VOCs, namely toluene, dichloromethane, acetaldehyde, methyl ethyl ketone (MEK), fert-butylcyclohexane, 1-decene, anethol, and limonene in aqueous solution at 30 ° C.
    Table 2
    VOCs Hcc Toluene 0.277 Dichloromethane 0.133 Acetaldehyde 0.006 Methyl ethyl ketone 0.007 tert-Butylcyclohexane 1.383 1-Decene 1.130 Anethol 0.031 Limonene 1,230
    As regards toluene, the Henry's constants determined for the DESs based on TBP and N4444Br are of the same order of magnitude as those obtained in ionic liquids and silicone oils.
    The results (value of Henry's constants (H cc ) and percentages of VOCs absorbed) for given ranges of concentration of initial VOCs, and at temperatures set at 30 ° C and / or 60 ° C, and this for different DES couples / VOCs are shown in the following table 3.
    Table 3
    cov OF Temperature(in ° C) Initial VOC concentration range tested (in g.m ' 3 ) Values of theHcc % absorbed ChCl: U 30 59-88 0.046 - 0.067 74-81 60 5.9 0.18 54 ChCl: G 30 59-235 0.022 - 0.042 81 - 89 Toluene 60 59 0.19 53 ChCl: EG 30 59-235 0.022- 0.028 87-90 ChCl: Lev 30 59-590 0.0026 - 0.0046 98-99 60 59 0.026 89 TBP: G 30 59-590 0.0021 -0.0049 98-99 60 59 0.0049 98 TBP: Lev 30 59-590 0-0.0015 99 - 100 60 59 0.0048 98 N 4 44 4 Br: Dec 30 59-590 0 - 0.0008 100 60 59 0.001 100 ChCl: U 30 59-590 0.044 - 0.077 71 - 83 60 5.9-59 0.12-0.23 45-62 ChCl: G 30 59-1176 0.030- 0.051 77-87 Dichloromethane 60 5.9-59 0.13-0.16 55-62 ChCl: EG 30 59-1176 0.028 - 0.059 76-87 ChCl: Lev 30 59-590 0.0073 - 0.0090 96 60 5.9-59 0.021 -0.028 88-90 TBP: G 30 59 0.0053 99 60 59 0.0059 99 TBP: Lev 30 59 0.0049 98 60 5.9-59 0 - 0.0002 100 N 4 44 4 Br: Dec 30 59-590 0.003 - 0.004 99 60 5.9-59 0 - 0.008 97 - 100
    cov OF Temperature(in ° C) Initial VOC concentration range tested (in g.m ' 3 ) Values of theHcc % absorbed Acetaldehyde ChCl: U 3060 59-117659-590 0.0002 - 0.00070.0003 - 0.0049 99.897.6 - 99.8 ChCl: G 3060 59-117659-590 0.0057 - 0.00640.0006-0.001 9799 ChCl: EG 30 59 0.0047 97.6 ChCl: Lev 3060 59-59059 0.0077-0.00910.059 9681 TBP: G 3060 59-59059-590 0.0002 - 0.00060.0001 -0.0003 99 - 10099 - 100 TBP: Lev 3060 59-59059-590 0.0097-0.0110.035 - 0.044 9582-85 N 4 44 4 Br: Dec 3060 59-59059 0.016-0.0180.058 9380 Methyl ethyl ketone (MEK) ChCl: U 30 29 - 235 0.0441 -0.0556 79 - 82 ChCl: EG 30 29 - 402 0.0180-0.0269 88-92 ChCl: G 30 29 - 470 0.0288 - 0.0425 82 - 88 ChCl: Lev 30 29- 1179 0.0072- 0.0083 96 TBP: EG 30 29 - 1352 0.0035 - 0.0039 98 Tert-Butylcyclohexane ChCl: Lev 30 29 - 343 0.0431 -0.0439 83 - 84 TBP-: EG 30 29 - 470 0 - 0.00052 100 1-Decene ChCl: EG 30 2.9-35 0.1328 -0.6028 60 ChCl: G 30 2.9-5.8 0.1667 -0.7032 25-55 ChCl: Lev 30 2.9 - 88 0 - 0.0455 82 TBP: EG 30 29-588 0 - 0.0007 100 Anethol ChCl: U 30 29 - 588 0.0007-0.0012 100 ChCl: EG 30 29 - 588 0.0003 -0.0015 100 ChCl: G 30 29 - 588 0.0014-0.003 100 ChCl: Lev 30 29 - 588 0.0001 -0.00021 100 Limonene ChCl: Lev 30 59 - 588 0 - 0.0205 89 - 100 TBP: EG 30 59 - 470 0-0.0011 100
    In quantitative terms, the inventors observed that the absorption capacity of the following DESs:
    - ChCl: U, ChCl: G, ChCl: EG, or
    -TBP: EG or TBP: G was at least 0.2 mg for toluene, 0.2 mg for dichloromethane and 0.3 mg for acetaldehyde per gram of DESs at 30 ° C and for a concentration of initial VOCs of 59 gm ' 3 at 30 ° C.
    The amount of VOC absorbed per gram of DES is calculated from the calibration line for VOC in water, allowing the concentration in the gas phase to be related to the area of the chromatographic peak thanks to the law of mass conservation and the Henry's constant. The amount of VOC introduced into the bottle being known, the amount trapped in the DES is obtained by the difference between the amount present in the gas phase and the initial amount. This value is reduced to 1 g of DES.
    In view of all these results, it appears that the absorption percentage is between 70% and 99% of the initial amount of VOCs added to the DESs.
    It is therefore demonstrated that the DESs suitable for the invention can be used both to absorb hydrophobic VOCs and hydrophilic VOCs.
    It also turns out that the DESs used are effective absorbents of VOCs at 30 ° C and 60 ° C.
    From these results, it is also found that certain pollutant / absorbent couples (VOC / DES) are particularly very effective insofar as the percentage of VOC absorbed is close to or even equal to 100%. These include toluene / TBP couples: Lev; toluene / N4444Br: Dec; dichloromethane / TBP: Lev; dichloromethane / N4444Br: Dec; acetaldehyde / TBP: G; fert-butylcyclohexane / TBP: EG; 1-decene / TBP: EG; anethol / ChCl: U; anethol / ChCl: EG; anethol / ChCl: G; anethol / ChCl: Lev; and limonene / TBP: EG.
    The trapping capacities of DESs were compared with those of four ionic liquids (LI), namely 1-butyl-l-methylpyrrolidinium dicyanamide, l-butyl-33058905 methylimidazolium acetate, l-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide and 1-butyl-1-methylpyrrolidinium (trifluoromethyl sulfonyl) imide.
    Table 4 summarizes the values of H cc and the percentage of VOCs (toluene and dichloromethane) absorbed for different LI / VOC couples at 30 ° C.
    Table 4
    VOC Ionic liquid initial VOC concentration tested in g.m ' 3 H cc values % absorbed Toluene 1-butyl-l-methylpyrrolidiniumdicyanamide 59 0.0027 98 l-butyl-3 -methylimidazolium acetate 59 0.0017 99 3-butyl-methylimidazolium bis (trifluoromethyl sulfonyl) imide 59 0.0007 99 1-butyl-l-methylpyrrolidinium(trifluoromethylsulfonyl) imide 59 0.0007 99 Dichloromethane 1-butyl-l-methylpyrrolidiniumdicyanamide 59 0.0047 98 l-butyl-3 -methylimidazolium acetate 59 0.0069 96 3-butyl-methylimidazolium bis (trifluoromethyl sulfonyl) imide 59 0.015 91 1-butyl-l-methylpyrrolidinium(trifluoromethylsulfonyl) imide 59 0.013 92
    From these results, it appears that the LI 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide and 1-butyl-1-methylpyrrolidinium (trifluoromethyl sulfonyl) imide have good capacities for toluene.
    However, among the LI tested l-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-l-methylpyrrolidinium dicyanamide and 1-butyl3-methylimidazolium bis (trifluoromethylsulfonyl) imide are classified as toxic and 1-butyl-l -methylpyrrolidinium bis (trifluoromethylsulfonyl) imide as an irritant.
    Consequently, although for some, the absorption capacities are of the same order of magnitude as for the DESs suitable for the invention, their application as washing solvents cannot be envisaged because of their toxicity.
    A main advantage of DESs is therefore to combine good absorption capacities of VOCs with non-toxicity (bio-sourced origin) and ease of synthesis.
    EXAMPLE 3 Impact of recycling of the absorbent solution containing at least one DES suitable for the invention on the absorption capacity
    A ChCl: U solution, prepared according to Example 1.1, is used, for the first time, to absorb toluene, the initial concentration of which is 59 g.m. 3 at a temperature of 30 ° C in accordance with the protocol set out in Example 2.
    After use, this absorbent solution is recycled by heating at a temperature of 60 ° C for 2 days to remove the VOCs absorbed.
    The ChCl: U solution recycled a first time is then used a second time to absorb toluene under the same conditions as above.
    Then, this solution is again recycled by heating at a temperature of 60 ° C for 2 days.
    Finally, the ChCl: U solution recycled a second time is then used a third time to absorb toluene under the same conditions as above.
    After comparing the values of the percentage of toluene absorbed by this same solution, it turns out that the absorption capacity is not affected in any way by the recycling of the solution. This is clearly demonstrated in Figure 2.
    EXAMPLE 4: Study in dynamic mode
    The trapping of VOCs in dynamic mode is carried out using an assembly composed of a syringe pump which delivers a known quantity of VOCs over time, a washing bottle containing the DES making it possible to bring the VOC into contact with the DES (this bottle can be filled with different DES volumes from 10 to 100 mL).
    Such an arrangement is illustrated in FIG. 3.
    The VOC concentration is measured by a total hydrocarbon analyzer (AHT). The amount of VOC trapped by the DES solution is obtained after desorption of the VOC by stripping (passage of air in the DES).
    EXAMPLE 5 Effect of Adding Cyclodextrins
    Two cyclodextrins, namely β-cyclodextrin and RAMEB are, independently of each other, added at different contents to a ChCl: El solution already prepared according to Example 1.1. The study of absorption in these solutions is carried out as described above for DESs alone (that is to say not associated with cyclodextrins).
    The effect of this addition is illustrated in FIG. 4 for toluene and a concentration of cyclodextrin of 0% (that is to say that the DES ChCl: El is "pure" in the sense that it is alone without presence cyclodextrin (s)), 2%, 4%, 8% and 10% by weight.
    The addition of cyclodextrin to ChCl: U has been found to improve its absorption capacity. This effect can be linked to the trapping capacities of cyclodextrins.
    EXAMPLE 6 Effect of adding water
    Different quantities of water are added to the DESs already synthesized in accordance with Example 1 and more particularly ChCl: U, ChCl: G, TBP: G and TBP: EG.
    The study of absorption in these solutions is carried out as described above for DESs alone.
    The effect of this addition is illustrated in Figure 5 for toluene and water contents of 0.5% and 5% by volume.
    It appears from these results that the presence of small amounts of water does not seem to affect the absorption capacities of DESs.
    Thus, the presence of moisture in the gaseous effluent has no effect on the absorption process.
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    1. Process for purifying a gaseous effluent containing at least one volatile organic compound (VOC), said process comprising at least the steps consisting in:
    (a) have at least one deep eutectic solvent (DES) comprising:
    (aa) at least one compound of formula (I) RiR 2 R3R4Y + X in which
    - Y is a nitrogen atom or a phosphorus atom;
    Ri, R 2 , R3 and R4 are independently of each other chosen from a hydrogen atom, a linear or branched C1-Cis alkyl, a linear or branched C1-C10 alkoxy, a C3-Cio cycloalkyl, a G, C10 or C7 to C12 aryl linear or branched aralkyl, said alkyl, alkoxy, cycloalkyl, aryl and aralkyl possibly being substituted by one or more substituents chosen from a hydroxyl group, a halogen atom, a group C 2 -C 10 acyl, SR5 group, NH 2 group, CN group, NO 2 group, CO2R5 group, CHO group, COR5 group and OR5 group, where R5 is selected from alkyl group Ci to Cis and a C3 to Cio cycloalkyl group; and
    - X is a halogen atom; and (bb) at least one compound (II) which is a hydrogen bond donor capable of forming a complex with X '; and (b) bringing said deep eutectic solvent of step (a) into contact with said gaseous effluent to be purified under conditions suitable for the absorption of said VOC by said DES.
    [2" id="c-fr-0002]
    2. Method according to claim 1, in which X is a chlorine, bromine, fluorine or iodine atom, preferably a chlorine or bromine atom.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, wherein Ri, R 2 , R3 and R4 are independently of each other chosen from a linear or branched C1-Cis alkyl optionally substituted by a hydroxyl group, preferably chosen from an alkyl in C 1 to C 4 linear optionally substituted by a hydroxyl group.
    [4" id="c-fr-0004]
    4. Method according to any one of the preceding claims, in which the compound of formula (I) is chosen from choline chloride, tetrabutylphosphonium bromide, tetrabutylammonium bromide, and mixtures thereof.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, in which the said compound (II) is chosen from levulinic acid, urea, ethylene glycol, glycerol, decanoic acid, an alkylene glycol, malonic acid, thiourea, N-methylurea, Ν, Ν'-dimethylurea, Ν, Ν-dimethylurea, acetamide, benzamide, 2,2,2trifluoroacetamide, imidazole, adipic acid, acid benzoic, benzyl alcohol, citric acid, phenol, // - methylphenol, o-methylphenol, m-methylphenol, / - chlorophenol, D-fructose, vanillin, oxalic acid , oxalic acid dihydrate, aniline, phenyl acetic acid, 3-phenylpropionic acid, succinic acid, tricarballylic acid, itaconic acid, xylitol, D-sorbitol, L- (+) - tartaric acid, Disosorbide, 4-hydroxybenzoic acid, caffeic acid, // - coumaric acid, trans-cinnamic acid, octanedioic acid, gallic acid, resorcinol, and mixtures thereof, preferably selected from levulinic acid, urea, ethylene glycol, glycerol, decanoic acid, and mixtures thereof.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which the deep eutectic solvent is chosen from choline chloride: urea, choline chloride: glycerol, choline chloride: ethylene glycol, choline chloride: levulinic acid , tetrabutylphosphonium bromide: glycerol, tetrabutylphosphonium bromide: levulinic acid, tetrabutylphosphonium bromide: ethylene glycol, tetrabutylammonium bromide: decanoic acid, and mixtures thereof, preferably chosen from choline chloride: urea, chloride choline: glycerol, choline chloride: ethylene glycol, choline chloride: levulinic acid, tetrabutylphosphonium bromide: glycerol, tetrabutylphosphonium bromide: levulinic acid, tetrabutylphosphonium bromide: ethylene glycol, and tetrabutom bromide decanoic.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, in which the deep eutectic solvent has a viscosity of less than 5,000 mPa.s, preferably ranging from 10 mPa.s to 1,000 mPa.s measured at 30 ° C.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, in which the molar ratio of compound (I) to compound (II) ranges from 1: 1 to 1: 12, preferably from 1: 1 to 1: 6.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, in which the volatile organic compound is chosen from:
    - alkanes, in particular ethane, propane, pentane, butane, isopentane, hexane, and fert-butylcyclohexane;
    - alkenes, in particular ethylene, propylene, 1-decene, and limonene;
    - arenas, in particular benzene, toluene, xylene, ethylbenzene, styrene, and anethole;
    - aldehydes, in particular formaldehyde, and acetaldehyde;
    - ketones, in particular methyl ethyl ketone and methyl isobutyl ketone;
    - esters, in particular methyl acetate, ethyl acetate, propyl acetate, and butyl acetate;
    - chlorinated volatile organic compounds, in particular dichloromethane, trichloromethane, tetrachloromethane, trichlorethylene, tetrachlorethylene and vinyl chloride e;
    - volatile organic sulfur compounds, in particular mercaptans and alkylsulfides, more particularly dimethylsulfide, dimethyldisulfide, and diethyl sulfide;
    - and their mixtures.
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, in which the volatile organic compound is chosen from toluene, dichloromethane, acetaldehyde, methyl ethyl ketone, tert-butyl cyclohexane, 1-decene, limonene, anethol and their mixtures, even more preferably from toluene, dichloromethane, acetaldehyde, methyl ethyl ketone, fert-butylcyclohexane, 1-decene, limonene, and anethole.
    [11" id="c-fr-0011]
    11. The method of claim 1, wherein said volatile organic compound and said deep eutectic solvent form a VOC / DES pair chosen from:
    - toluene / TBP: Lev;
    - toluene / N4444Br: Dec;
    - toluene / TBP: G;
    - toluene / ChCl: Lev; dichloromethane / TBP: Lev;
    - dichloromethane / N4444Br: Dec; dichloromethane / TBP: G;
    - acetaldehyde / TBP: G;
    - acetaldehyde / ChCl: U;
    - acetaldehyde / ChCl: G; methyl ethyl ketone / TBP: EG; fert-butylcyclohexane / TBP: EG;
    - 1-decene / TBP: EG;
    - Anethole / ChCl: U;
    - Anethole / ChCl: EG;
    - Anethole / ChCl: G;
    Anethol / ChCl: Lev;
    Limonene / ChCl: Lev; and Limonene / TBP: EG.
    preferably chosen from:
    - toluene / TBP: Lev;
    - toluene / N4444Br: Dec;
    - dichloromethane / TBP: Lev;
    - dichloromethane / N4444Br: Dec;
    - acetaldehyde / TBP: G; fert-butylcyclohexane / TBP: EG;
    - 1-decene / TBP: EG;
    - Anethole / ChCl: U;
    - Anethole / ChCl: EG;
    - Anethole / ChCl: G;
    - Anethole / ChCl: Lev; and Limonene / TBP: EG.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, further comprising, following step (b), recovering said gaseous effluent depleted in VOCs and preferably devoid of VOCs.
    [13" id="c-fr-0013]
    13. Method according to any one of the preceding claims, characterized in that it is implemented in continuous, semi-continuous or batch mode.
    [14" id="c-fr-0014]
    14. Method according to any one of the preceding claims, characterized in that it is implemented by circulation, preferably in a closed loop.
    [15" id="c-fr-0015]
    15. Method according to any one of the preceding claims, characterized in that the gaseous effluent to be purified has a flow rate between 100 m 3 / h and 100,000 m 3 / h, preferably between between 100 m 3 / h and 10,000 m 3 / h and an initial concentration of VOCs between 1 g.m ' 3 and 10,000 g.m' 3 , preferably between 2.9 g.m ' 3 and 1180 g.m' 3 .
    [16" id="c-fr-0016]
    16. Use of at least one deep eutectic solvent as defined in any one of claims 1 to 8 to absorb at least one volatile organic compound as defined in any one of claims 1, 9 and 10 contained in a gaseous effluent.
    [17" id="c-fr-0017]
    17. Composition comprising at least one volatile organic compound as defined in any one of claims 1, 9 and 10 and at least one deep eutectic solvent as defined in any one of claims 1 to 8.
    [18" id="c-fr-0018]
    18. Composition according to the preceding claim, in which said volatile organic compound is present therein in a form absorbed to said deep eutectic solvent.
    [19" id="c-fr-0019]
    19. The composition as claimed in claim 17 or claim 18, further comprising at least one cyclodextrin chosen from α-cyclodextrins, β-cyclodextrins, γcyclodextrins, substituted or not, and their mixtures, preferably chosen from a β5 cyclodextrin, RAMEB, and their mixtures, and even more preferably chosen from a β-cyclodextrin and RAMEB.
    1/3
    W® water *
    OF
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1661212|2016-11-18|
    FR1661212A|FR3058905B1|2016-11-18|2016-11-18|PROCESS FOR THE PURIFICATION OF A GASEOUS EFFLUENT|FR1661212A| FR3058905B1|2016-11-18|2016-11-18|PROCESS FOR THE PURIFICATION OF A GASEOUS EFFLUENT|
    PCT/EP2017/078950| WO2018091379A1|2016-11-18|2017-11-10|Process for purifying a gaseous effluent|
    EP17804829.4A| EP3541496B1|2016-11-18|2017-11-10|Process for purifying a gaseous effluent|
    CN201780081007.2A| CN110114129A|2016-11-18|2017-11-10|The purification method of gaseous effluent|
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