REMOVAL OF IMPURITIES WITHIN AN ORGANIC PEROXIDE

Abstract

ELIMINATION OF IMPURITIES WITHIN AN ORGANIC PEROXIDE The present invention relates to the use of a zeolitic adsorbent material, to purify organic peroxides, and more particularly to eliminate the impurities present in these compositions of organic peroxides.

Description

Title of the invention: REMOVAL OF IMPURITIES WITHIN AN ORGANIC PEROXIDE

[0001] The present invention relates to the field of purification of organic peroxides.

[0002] The invention relates in particular to the use of zeolitic adsorbent materials to purify organic peroxides, and more particularly to eliminate impurities present in these compositions of organic peroxides.

[0003] The invention also relates to a method for purifying an organic peroxide composition, aimed in particular at eliminating impurities present in this organic peroxide composition.

[0004] Organic peroxides are commonly used as initiators of ethylenically unsaturated monomer polymerization for the synthesis of various types of polymers, for example halogenated vinyl polymers, such as polyvinyl chloride.

[0005] In this field, very high-purity organic peroxides are sought. Two technical solutions can be implemented to increase the purity of these products. It is possible to work on the organic peroxide synthesis process to improve the performance of each step, or it is possible to work directly on the finished product. In other words, this latter possibility consists of increasing the purity of the organic peroxide.

[0006] However, organic peroxides are most often highly unstable species, as they decompose relatively easily under the influence of a small amount of heat, mechanical energy (friction or impact), and / or incompatible contaminants. Thus, in the event of an uncontrolled rise in their storage temperature, some organic peroxides can undergo self-accelerating exothermic decomposition, which can lead to fires and / or violent explosions. Furthermore, under these conditions, some of these organic peroxides can release combustible vapors capable of reacting with any ignition source, which can drastically increase, or even accelerate, the risk of a violent explosion.

[0007] Often, organic peroxide compositions contain impurities resulting from their synthesis process. These impurities may be alcohols, olefins, ketones, acids, or other peroxides such as hydroperoxides, dialkyl peroxides, and perketals. It is known to remove these alcohols by hot air or steam stripping, pervaporation, extraction, or distillation. However, these methods often lead to a significant loss of organic peroxide, or to a decomposition of the organic peroxide due to its instability.

[0008] US patent 5453548 teaches the use of acid zeolites to separate di-tert-butyl peroxide from a mixture containing tert-butanol. The catalytic action of the acid zeolites allows at least partial dehydration of the tert-butanol into isobutylene and water. The di-tert-butyl peroxide with a low tert-butanol content is then separated from the isobutylene and water formed.

[0009] This step of separating isobutylene and water is carried out at a temperature above 80°C, in particular by distillation, which may present certain risks due to the possible degradation of the organic peroxide.

[0010] It is also known from US patent 5792890 to use basic zeolites to purify butyl tertiary alcohol contaminated with corrosive oxygen-containing impurities, such as peroxides. This patent states that basic zeolites that act as catalysts and decompose these impurities, particularly peroxides, are zeolites with a Si / Al ratio greater than 5.00.

[0011] A method for purifying organic peroxide compositions is thus sought, and more particularly a method for removing impurities, and especially a method for removing alcohol(s) and / or hydroperoxides, that is easy to implement and safer. The aim is to avoid accidents related to the instability of organic peroxides and to prevent their degradation. This method for removing impurities from organic peroxide compositions must also be satisfactory in terms of yield. Obviously, this method must not generate other impurities or damage the treated organic peroxide.

[0012] It has now been surprisingly discovered that the aforementioned objectives can be achieved through the use of specific zeolitic adsorbent materials. These specific zeolitic adsorbents allow for the specific adsorption of impurities, particularly alcohols and / or hydroperoxides and / or olefins and / or ketones and / or acids, and especially alcohols and / or hydroperoxides in organic peroxide compositions, without substantially degrading said organic peroxides or the adsorbed impurities.

[0013] The invention relates to the use of a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and more preferably between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals, alone or in mixture, to remove impurities, in particular alcohols and / or hydroperoxides and / or olefins. and / or ketones and / or acids, and more preferably alcohols and / or hydroperoxides, in an organic peroxide composition.

[0014] The invention also relates to a method for removing impurities, in particular alcohols and / or hydroperoxides and / or olefins and / or ketones and / or acids, and more preferably alcohols and / or hydroperoxides, especially present as impurities, in one or more organic peroxides, comprising at least one step of contacting said organic peroxide composition with a zeolitic adsorbent material as defined above.

[0015] It has been observed that impurities, in particular alcohol(s) and / or hydroperoxide(s) and / or olefin(s) and / or ketone(s) and / or acid(s), and more preferably alcohol(s) and / or hydroperoxide(s), present in the organic peroxide composition, are adsorbed by these specific zeolite materials. Thus, the single step of contacting the specific zeolite material with the composition comprising the organic peroxide allows for the trapping of impurities, in particular alcohol(s) and / or hydroperoxide(s) and / or olefin(s) and / or ketone(s) and / or acid(s), and more preferably alcohol(s) and / or hydroperoxide(s). The use of these materials avoids a subsequent distillation step, as described in the process of US patent 5453548.The use according to the invention thus allows a single step of bringing the organic peroxides into contact with the zeolitic adsorbent material.

[0016] Furthermore, the use according to the invention can be carried out at all temperatures, and preferably at ambient temperature or at a temperature lower than ambient temperature, preferably at ambient temperature, in particular for reasons of process cost control, provided that the peroxide does not degrade at this temperature, which has an advantage in terms of ease of implementation and in terms of safety.

[0017] Other features, aspects, objects and advantages of the present invention will become even clearer upon reading the following description.

[0018] It is specified that the expressions "from ... to ..." and "between ... and ..." used in this description should be understood as including each of the limits mentioned.

[0019] Use

[0020] The use according to the invention makes it possible to eliminate at least one impurity, in particular selected from the group consisting of one or more alcohols, one or more hydroperoxides, one or more olefins, one or more ketones, one or more acids and mixtures thereof, preferably selected from the group consisting of one or more alcohols, one or more hydroperoxides, one or more olefins, one or more ketones and mixtures of these and more preferably one or more alcohols and / or one or more hydroperoxides present in the composition of organic peroxide.

[0021] Composition of organic peroxide to be purified

[0022] By "organic peroxide composition" is meant a composition comprising one or more organic peroxides.

[0023] Preferably, the organic peroxide(s) represent at least 50% by weight, preferably 80% by weight, preferably at least 90% by weight, even more preferably 95% by weight of the composition before purification.

[0024] Organic peroxides

[0025] For the purposes of this invention, "organic peroxide" means a chemical compound containing at least one functional group of general formula COOC.

[0026] Organic peroxides are preferably chosen from peroxyesters, monoperoxycarbonates, dialkyl peroxides, peroxyketals, diacyl peroxides, diperoxycarbonates, hydroperoxides and mixtures thereof, and more preferably from peroxyesters, monoperoxycarbonates, dialkyl peroxides, diacyl peroxides, peroxyketals and mixtures thereof.

[0027] Preferably, the organic peroxide is a monoperoxycarbonate corresponding to the following formula (I):

[0028] [Chem.l] R2 .O- 'K f "CT Y 4L 4 œ O

[0029] in which Ri and R2 represent, independently of each other, saturated or unsaturated, linear, branched or cyclic alkyl radicals, in C1-C1. Preferably, Ri and Re represent, independently of each other, saturated, linear or branched alkyl radicals, in C2-C1.

[0030] Preferably, Ri represents a saturated alkyl radical, linear or branched, in C2-Ci0.

[0031] Preferably, R2 represents a saturated alkyl radical, linear, branched or cyclic, in C4-C20.

[0032] Preferably, Ri represents a saturated alkyl radical, linear or branched, in C2-C1 and R2 represents a saturated alkyl radical, linear, branched or cyclic, in C4-C 10-

[0033] Preferably, the monoperoxycarbonate of formula (I) is chosen from the group consisting of OO-tert-amyl-O-(2-ethylhexyl) monoperoxycarbonate (TAEC), OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate (TBEC), OO-tert-octyl-O-(2-ethylhexyl) monoperoxycarbonate (TOEC), the OO-tert-hexyl-O-(2-ethylhexyl) monoperoxycarbonate (THEC), tert-amylperoxyisopropyl monocarbonate (TAIC), tert-amylperoxy-n-propyl monocarbonate (TAPC), tert-butylperoxyisopropyl monocarbonate (TBIC), tert-octylperoxyisopropyl monocarbonate (TOIC), tert-hexylperoxyisopropyl monocarbonate (THIC), and mixtures thereof. Some of the monoperoxycarbonates mentioned above and conforming to the invention are available under the trade names Luperox® or Lupersol®, sold by Arkema.

[0034] Preferably, the monoperoxycarbonate of formula (I) corresponds to OO-tert-amyl-O-(2-ethylhexyl) monoperoxycarbonate (TAEC) or to OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate (TBEC), and more particularly to OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate (TBEC).

[0035] Preferably, the organic peroxide is a peroxyester corresponding to the following formula (II):

[0036] [Chem.2] ° (II)

[0037] in which R3 and R4, identical or different, represent a CrC2o hydrocarbon chain, linear, branched or cyclic, saturated or able to comprise one or more unsaturations, able to comprise one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally substituted by one or more hydroxyl groups.

[0038] Preferably, R3 represents a Ci-C20 hydrocarbon chain, preferably Ci-Cio, linear or branched or cyclic, unsaturated or saturated, which may comprise one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally substituted by one or more hydroxyl groups.

[0039] Preferably, R4 represents a C4-C20 hydrocarbon chain, preferably C4-C8, linear or branched or cyclic, saturated or unsaturated.

[0040] The peroxyester is preferably selected from α-cumylperoxyneodecanoate, α-cumylperoxyneoheptanoate, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, tert-butylperoxy-n-heptanoate, tert-butylperoxyneodecanoate, α-cumylperoxy-n-heptanoate, tert-amylperoxy-n-heptanoate, tert-butylperoxyneoheptanoate, 2,5-dimethyl-2,5-di-(2-ethylhexanoylperoxy)hexane, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylp 2-ethylhexanoate, hydroxyperoxyesters, tert-amylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxypivalate, tert-hexylperoxyneodecanoate, tert-hexylperoxypivalate, tert-amylperoxypivalate, tert-butylperoxypivalate, tert-amylperoxyacetate, tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butylperoxy-3,5,5-trimethyllexanoate, tert-amylperoxy-3,5,5-trimethylhexanoate, and mixtures thereof. Some of the peroxyesters mentioned above and conforming to the invention are available under the trade name Luperox® sold by the company Arkema.

[0041] Preferably, the peroxyester is chosen from tert-butylperoxyneodecanoate, tert-amylperoxypivalate, tert-butylperoxypivalate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-amylperoxy-3,5,5-trimethylhexanoate and mixtures thereof, and more particularly tert-butylperoxy-3,5,5-trimethylhexanoate, tert-amylperoxy-3,5,5-trimethylhexanoate and mixtures thereof.

[0042] Preferably, the organic peroxide is a dialkyl peroxide corresponding to the following formula (III):

[0043] [Chem.3] 5 .......O.... 6

[0044] In which R5 and R6, identical or different, represent a saturated Ci-C20 hydrocarbon chain, linear, branched or cyclic.

[0045] Preferably, R5 represents a C4-C2o hydrocarbon chain, preferably C4-C10, linear or branched or cyclic, unsaturated or saturated.

[0046] Preferably, R6 represents a C4-C2o hydrocarbon chain, preferably C4-Cio, linear or branched or cyclic, saturated or unsaturated.

[0047] The dialkyl peroxide is preferably chosen from di-tert-butyl peroxide, di-tert-amyl peroxide, cumyl and tert-butyl peroxide, di-cumyl peroxide.

[0048] Di-alkyl peroxides can also comprise two peroxide functions and then correspond to the formula (Illb) in which the structure X represents a branched or cyclic alkyl structure, saturated or unsaturated in C6-Ci6.

[0049] [Chem.4] rL O.. _ CL R'6 Ullb)

[0050] Preferably, the dialkyl peroxide of this structure is chosen from dimethyl-tert-butylperoxyhexane, bis(tert-butylperoxyisopropyl)benzene.

[0051] Preferably, the organic peroxide is a diacyl peroxide corresponding to the following formula (IV):

[0052] [Chem.5] q ■zJk. .0. ,RS R '0' V ô (IV)

[0053] In which R7 and R8, identical or different, represent a C6-C2o hydrocarbon chain, linear, branched, saturated or unsaturated.

[0054] Preferably, R7 represents a C6-C2o hydrocarbon chain, preferably C6-Ci2, linear or branched, unsaturated or saturated.

[0055] Preferably, R8 represents a C6-C20 hydrocarbon chain, preferably C6-Ci2, linear or branched, saturated or unsaturated.

[0056] Preferably, the diacyl peroxide of this structure is chosen from dilauroyl peroxide, didecanoyl peroxide, diheptanoyl peroxide, dioctanoyl peroxide and disuccinoyl peroxide.

[0057] Preferably, the organic peroxide is a peroxyketal corresponding to the following formula (V):

[0058] [Chem.6] XR " (y)

[0059] In which R9 and Rn, identical or different, represent a saturated, linear or branched C4-C10 hydrocarbon chain.

[0060] Preferably, R10 and Rn represent a saturated, linear or branched C3-Ci2, preferably C3-C9, hydrocarbon chain. R10 and Ru may also be part of a cyclic hydrocarbon structure.

[0061] Preferably, the diacyl peroxide of this structure is chosen from 2,2-di(tert-butylperoxy)butane, 2,2-di(tert-amylperoxy)butane, 2,2-di(tert-butylperoxy)propane,

[0062] 2,2-di(tert-amylperoxy)propane, l,l-di(tert-butylperoxy)cyclohexane, l,l-di(tert- amyl peroxy) cyclohexane and l,l-di(tert-butyl peroxy)-3,3,5-trimethylcyclohexane.

[0063] Preferably, the organic peroxide is a monoperoxycarbonate.

[0064] Impurity

[0065] For the purposes of this invention, "impurities" means any compound other than the organic peroxide to be purified or water present in the composition of organic peroxide.

[0066] Preferably, the impurity(ies) to be eliminated is / are chosen from the group consisting of: alcohols, hydroperoxides, olefins, ketones, acids, and mixtures thereof, and more preferably alcohols, hydroperoxides, and mixtures thereof.

[0067] Alcohol

[0068] Preferably, the alcohol is a compound of formula ROH in which R represents: - a linear or branched alkyl group, saturated or unsaturated, in CrCi6, preferably in C2-Ci0, optionally substituted by an aromatic group, - an aromatic group; or - a ring, preferably at C6, possibly substituted by one or more alkyl groups, preferably branched, preferably at C3 or C4. Preferably, R represents a linear or branched, saturated alkyl group, in Ci-Cio, preferably in C2-Ci0.

[0069] Preferably, the alcohol is chosen from the group consisting of 2-ethylhexanol, methanol, ethanol, n-propanol, n-butanol, n-hexanol, n-octanol, allyl alcohol, i-propanol, i-butanol, diethylene glycol, phenol, benzyl alcohol, menthol and mixtures thereof, preferably 2-ethylhexanol.

[0070] Hydroperoxide

[0071] Preferably, the hydroperoxide is a compound of formula ROOH, preferably a compound corresponding to formula (VI):

[0072] [Chem.7] 2 R.. O ' H (ypy

[0073] Formula (VI) in which R2 is as defined above;

[0074] Preferably, R2 represents saturated alkyl radicals, linear or branched, in the C4-C2O range. Preferably, R2 represents a saturated alkyl radical, linear or branched, in the C4-C2O range.

[0075] Preferably, R2 represents a saturated alkyl radical, linear or branched, in C4-Cio.

[0076] Preferably, the hydroperoxide is chosen from the group consisting of: t-butyl hydroperoxide (TBHP), t-amyl hydroperoxide (TAHP), t-hexyl hydroperoxide (THHP), 1,1,3,3-tetramethylbutyl hydroperoxide (TOHP), paramenthane hydroperoxide (PMHP), cumyl hydroperoxide, 2,5- dimethyl-2,5-dihydroperoxide (2,5-2,5) and mixtures thereof, preferably is chosen from the group consisting of: t-butyl hydroperoxide and t-amyl hydroperoxide, again preferably is t-butyl hydroperoxide.

[0077] Olefin

[0078] Preferably, the olefin is a linear, branched or cyclic hydrocarbon compound containing at least one unsaturation. Preferably, the olefin is selected from the group consisting of: butenes, pentenes, hexenes, heptenes, octenes, nonenes, decenes, dodecenes, α-methylstyrene, diisopropenylbenzenes and mixtures thereof.

[0079] Ketone

[0080] Preferably, the ketone is a compound of formula RaCORb corresponding to the following formula (VII):

[0081] [Chem. 8] O

[0082] wherein Raet Rb, identical or different, represent a Ci-Ci6 hydrocarbon chain, linear, branched, cyclic, saturated or unsaturated.

[0083] Preferably, the Ra and Rb structures independently represent: - a linear or branched alkyl group, saturated or unsaturated, in the C1-C16 configuration, preferably in the C2-C10 configuration, possibly substituted by an aromatic group, - an aromatic group; or - the two Ra and Rb structures can form a ring, preferably at C6, possibly substituted by one or more alkyl groups, preferably branched, preferably at C3 or C4. Preferably, the ketone is chosen from the group consisting of: acetone, methylethylketone, acetophenone, methyl-isobutylketone, isopropylacetophenone, cyclohexanone, trimethylcyclohexanone, and mixtures thereof.

[0084] Acid

[0085] Preferably, the acid is a carboxylic acid of the following formula RcCOOH (VIII):

[0086] [Chem.9]

[0087] Preferably, ^ represents saturated alkyl radicals, linear or branched, in C1-C2O. Preferably, Rc represents a saturated alkyl radical, linear or branched, in C4-C12

[0088] Preferably, R2 represents a saturated alkyl radical, linear or branched, in C6-Cio.

[0089] Preferably, the acid is chosen from the group consisting of: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, ethyl-2-hexanoic acid, neodecanoic acid, decanoic acid, pivalic acid, trimethylhexanoic acid, lauric acid and mixtures thereof.

[0090] Neolithic adsorbent material

[0091] The use according to the invention involves a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and preferably still between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals, alone or in mixture.

[0092] Preferably, the molar ratio of sodium oxide to the sum of all the alkali and / or alkaline-earth oxides of the zeolitic adsorbent material is between 0 and 0.99, preferably between 0 and 0.98, preferably still between 0 and 0.97, and more particularly between 0 and 0.95, inclusive.

[0093] The zeolite adsorbent material according to the present invention is a faujasite-type zeolite-based adsorbent, including hierarchically porosity faujasite-type zeolites (zeolites comprising mesopores and micropores), as described for example in applications WO2015019013, WO2015019014, WO2015028740, and WO2015028741. Hierarchically porosity faujasite-type zeolites (known as "ZPH") are generally obtained by direct synthesis, in particular using sacrificial agents, as described for example in applications WO2015019013 or WO2007043731, or by surface post-treatment, as described for example in WO2013106816.

[0094] The zeolitic adsorbent material according to the present invention has an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and preferably still between 1.00 and 3.00.

[0095] Advantageously, the zeolitic adsorbent material according to the invention comprises one or more zeolites of faujasite structure selected from zeolites of type LSX, MSX, X and Y, and preferably of type LSX, MSX and X.

[0096] By LSX zeolite, meaning in English Low Silica X, is meant a zeolite with an atomic Si / Al ratio of 1 ± 0.05. By MSX zeolite, meaning in English In English, Medium Silica X refers to a zeolite whose Si / Al atomic ratio is such that 1.05 < Si / Al < 1.15. Zeolite X, on the other hand, is characterized by an atomic ratio of Si / Al such that 1.15 < Si / Al < 1.50. Zeolite Y is characterized by an atomic ratio of Si / Al such that 1.50 < Si / Al < 3.00.

[0097] For the purposes of the present invention, mixtures of two or more zeolites, in any proportion, can be used as zeolitic adsorbent materials.

[0098] The zeolites listed above can be used in their "native" form, i.e., as crystals, but are preferably used as agglomerates of zeolite crystals with one or more binders, according to techniques well known to those skilled in the art, and in particular by agglomerating zeolite crystals with an agglomerating binder. The agglomerating binder can be of any type that allows the agglomeration and cohesion of the zeolite crystals and is generally chosen from clays, including, but not limited to, kaolin, kaolinite, attapulgite, sepiolite, bentonite, and others, as well as mixtures of two or more of these clays, in any proportion.

[0099] Zeolite crystals are thus advantageously agglomerated with at least one agglomeration binder, and, if necessary or desired, one or more additives well known to those skilled in the art, before being dried and / or baked and / or calcined.

[0100] Preferably, the zeolite adsorbent material according to the invention comprises more than 50% by weight, relative to the total weight of the material, of a faujasite-type (structure) zeolite, advantageously more than 80% by weight, preferably more than 90% by weight, and particularly preferably more than 95% by weight. In other words, the zeolite adsorbent material according to the invention comprises more than 50% by weight of a faujasite-type zeolite relative to the total weight of the zeolite adsorbent material, advantageously more than 80% by weight, preferably more than 90% by weight, and particularly preferably more than 95% by weight of a faujasite-type zeolite, relative to the total weight of the zeolite adsorbent material.

[0101] Additives are also well known to those skilled in the art. Their nature and quantity added can vary greatly depending on the desired or required effect. Examples of additives that can be used with agglomerating binders include, but are not limited to, surface passivation additives intended to manage the surface reactivity of agglomerates and / or improve their separation selectivity, for example tetrasodium pyrophosphate (TSPP), rheological additives, granulation additives, and others, as well as mixtures of two or more of them.

[0102] Agglomerated zeolite crystals can also be engaged in a zeolithization operation, also well known to those skilled in the art, This involves transforming all or part of the agglomerating binder into zeolitic crystalline material in order to increase the adsorption capacity of said agglomerates. The techniques for agglomerating zeolite crystals, drying, baking, calcining, and zeolithization are thoroughly described in the scientific and patent literature, for example in applications WO1999010096 and WO2000050166.

[0103] The presence of metallic cations (alkaline and / or alkaline-earth) in the zeolitic adsorbent materials usable within the framework of the present invention results either directly from the synthesis of said adsorbent materials, in particular the sodium cation for zeolites prepared from sodium solutions, or by one or more cation exchange operations, according to classic techniques well known to those skilled in the art, said exchanges being able to be carried out on the initial zeolite crystals and / or on the agglomerates of zeolite crystals, before and / or during and / or after their shaping, preferably before and / or after their shaping.

[0104] The zeolite adsorbent material according to the present invention comprises one or more alkali and / or alkaline earth metals, alone or in mixtures, in the form of cations that ensure the electronic neutrality of the zeolite structure. The alkali and / or alkaline earth metal contents of said zeolite adsorbent material are determined by elemental chemical analysis expressed as oxides of each of said alkali and / or alkaline earth metals.

[0105] Preferably, the molar ratio of sodium oxide to the sum of all the alkali and / or alkaline-earth oxides of the zeolitic adsorbent material is between 0 and 0.99, preferably between 0 and 0.98, preferably still between 0 and 0.97, and more particularly between 0 and 0.95, inclusive.

[0106] In other words, in this embodiment, the zeolite adsorbent material cannot comprise 100% sodium, expressed as a mole of sodium oxide. In further terms, in this embodiment, the zeolite adsorbent material cannot comprise sodium oxide as the sole alkali and / or alkaline earth oxide. It may contain sodium, but only when mixed with one or more other alkali and / or alkaline earth metals, that is, in a molar ratio of sodium oxide to the sum of all the alkali and / or alkaline earth oxides in the zeolite adsorbent material that is between 0 and 0.99.

[0107] The zeolitic adsorbent material may comprise 100% by mole of alkali metals, other than sodium, and / or alkaline earth metals.

[0108] The zeolitic adsorbent material according to the present invention may thus comprise one or more alkali and / or alkaline earth metals selected from the group consisting of: sodium (Na), barium (Ba), calcium (Ca), potassium (K), magnesium (Mg), strontium (Sr), lithium (Li), cesium (Cs) and mixtures of two or more of them in any proportions.

[0109] Preferably, the zeolite adsorbent material comprises at least one zeolite selected from the group consisting of: NaKLSX, NaBaLSX, NaLiLSX, LiLSX, BaLSX, BaKLSX, NaCaLSX, CaBaNaLSX, NaKMSX, NaBaMSX, NaLiMSX, LiMSX, BaMSX, BaKMSX, NaCaMSX, CaBaNaMSX, BaX, NaX, NaBaX, BaKX, NaCaX, CaBaNaX, BaY, NaY, NaKY, KY, BaKY, NaBaY, CaBaNaY and mixtures thereof, preferably selected from the group consisting of: NaKLSX, NaBaLSX, NaLiLSX, LiLSX, BaLSX, BaKLSX, NaCaLSX, CaBaNaLSX, BaX, NaBaLSX, BaKX, NaCaX, CaBaNaX, BaY, NaKY, BaKY, and mixtures thereof, preferably chosen from the group consisting of NaKLSX, NaBaLSX, NaLiLSX, LiLSX, BaLSX, BaKLSX, NaCaLSX, CaBaNaLSX, BaX, NaBaLSX, BaKX, NaCaX, CaBaNaX, BaY, NaKY, BaKY, and their mixtures again preferably chosen from the group consisting of BaLSX, KY, and BaX.

[0110] Preferably, the zeolitic adsorbent material has a loss on ignition (LOI) of less than 15%, preferably less than 10%, and preferably less than 8% by weight.

[0111] Preferably, the zeolitic adsorbent material has a loss on ignition greater than 0.5% by weight, preferably greater than 1% by weight, even more preferably greater than 1.5% by weight.

[0112] Preferably, the zeolitic adsorbent material has a loss on ignition of between 0.5% and 15%, preferably between 1% and 10%, more preferably between 1.5% and 8% by weight inclusive.

[0113] For the purposes of the present invention, "loss on ignition" means the percentage of mass loss following calcination. Preferably, the loss on ignition is determined in an oxidizing atmosphere, by calcining the sample in air at a temperature of 900°C ± 25°C, according to standard NF EN 196-2 (April 2006).

[0114] Preferably, the mass ratio between the impurity to be removed and the zeolitic adsorbent material is between 1:5 and 1:60, preferably between 1:10 and 1:50.

[0115] The zeolitic adsorbent material usable within the framework of the present invention can indeed, if necessary or desired, and most often, be shaped, according to any technique known to the person skilled in the art, and in particular by extrusion, granulation, and others, for shaping of the type beads, yarns, and others, such as for example monolithic solids and membranes.

[0116] The use according to the invention is thus aimed at adsorbing the impurity or impurities into the zeolitic adsorbent material.

[0117] Advantageously, the use of the zeolitic material defined above to remove the impurity or impurities, in an organic peroxide composition is carried out at a temperature between -20°C and +50°C, preferably between +2°C and +50°C, even more preferably between +5°C and +40°C.

[0118] When the zeolite material is brought into contact with the organic peroxide composition, the impurity or impurities, in particular the alcohol(s) and / or hydroperoxide(s) and / or olefin(s) and / or ketone(s) and / or acid(s), and more preferably the alcohol(s) and / or hydroperoxide(s), are adsorbed into the zeolite material. In other words, the contact is an adsorption step of the impurity or impurities, in particular the alcohol(s) and / or hydroperoxide(s) and / or olefin(s) and / or ketone(s) and / or acid(s), and more preferably the alcohol(s) and / or hydroperoxide(s).

[0119] Preferably, the removal of impurities is carried out by this single step of bringing into contact between the organic peroxide composition to be treated and the zeolitic adsorbent material as described above.

[0120] The invention relates to the use of a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and even more preferably between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals, alone or in mixture, in particular to remove impurities, in an organic peroxide composition.

[0121] Preferably, the use according to the invention relates to the use of the zeolitic adsorbent material as described above to remove 2-ethylhexanol from OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate (TBEC).

[0122] Preferably, the use according to the invention relates to the use of the zeolitic adsorbent material as described above to remove 2-ethylhexanol from OO-tert-amyl-O-(2-ethylhexyl) monoperoxycarbonate (TAEC).

[0123] Process

[0124] The process for removing one or more impurities, in particular one or more alcohols and / or one or more hydroperoxides and / or one or more olefins and / or one or more ketones and / or one or more acids, more preferably one or more alcohols and / or one or more hydroperoxides, from an organic peroxide composition, according to the present invention, comprises at least one step in which the organic peroxide composition is contacted with a zeolitic adsorbent material as defined above. It should be understood that the process of the present invention utilizes one or more zeolitic adsorbent materials as defined above.

[0125] This contacting step can advantageously be carried out at a temperature between -20°C and +50°C, preferably between +2°C and +50°C, even more preferably between +5°C and +40°C, more particularly, the process is carried out at room temperature.

[0126] Similarly, the contacting step can be carried out under pressure, at atmospheric pressure, or under vacuum, or even under vacuum. However, it is preferable to operate at atmospheric pressure, or under pressure up to 20 bar (2 MPa), preferably 2 bar (200 kPa), and most preferably under atmospheric pressure, i.e., at the working pressure, and more specifically without the introduction of any pressure or vacuum, apart from the pressure differences provided by equipment such as pumps, valves and the like, for reasons of economy in the process of the invention.

[0127] Advantageously, the contacting step is carried out at a temperature between -20°C and +50°C, preferably between +2°C and +50°C, even more preferably between +5°C and +40°C, at atmospheric pressure.

[0128] The contact time can vary considerably, depending in particular on the nature and quantity of the impurities to be removed, the nature and quantity of the zeolitic adsorbent material used, and the type of contacting system used. Furthermore, the contact time varies depending on the temperature and pressure applied.

[0129] Contact with the zeolitic adsorbent material can be carried out by any method well known to those skilled in the art, continuously or in batches, and for example by forced (pumps) or gravity passage of the liquid through said zeolitic adsorbent material, such as in a packed column, or by simple contact in a reactor, such as a reactor equipped or not with an agitation system, and other.

[0130] More specifically, the step in the process of bringing the organic peroxide composition to be purified into contact with at least one zeolitic adsorbent material can be implemented in various static (or batch), dynamic, semi-continuous or continuous processes.

[0131] The contacting step can thus be carried out in one or more stages, in batch and / or statically, in storage drums, with or without agitation, dynamically or continuously. Preferably, this purification step takes place before any storage stage of the liquid to be treated and preferably dynamically through a bed of adsorbent, preferably through a fixed bed of adsorbent. Thus, and by way of non-limiting examples, the contacting step of the process of the invention can be carried out in batch, and in this case, one embodiment consists of depositing a bed of adsorbent at the bottom of the container in which the organic peroxide to be purified is stored, for a The duration varies depending on the content and nature of the impurity to be removed. This duration can indeed vary considerably, and is generally between a few minutes and a few days, for example between 1 hour and 48 hours, preferably between 1 hour and 10 hours.

[0132] Alternatively, the contact step can be carried out continuously, according to any known dynamic process, in which the liquid to be purified passes through a bed of zeolitic adsorbent material under the temperature and pressure conditions indicated above. The continuous flow rate of said liquid through said adsorbent bed can vary considerably depending on the degree of purity and the nature of the impurities to be removed, but is generally adapted to allow a contact time typically ranging from a few minutes to a few days, for example, between 1 hour and 48 hours. The bed of zeolitic adsorbent material can be of any type well known to those skilled in the art, and in particular a fixed bed, a fluidized bed, or a moving bed (simulated or not).In the case of continuous contact, it is preferable to implement a fixed bed with regeneration of the zeolitic adsorbent material or operation with two adsorbers, the first working in adsorption and the second working in desorption / regeneration.

[0133] According to a particularly advantageous embodiment of the invention, the zeolitic adsorbent material can indeed be desorbed and / or regenerated, in batch or continuously, according to conventional desorption and regeneration techniques, and in particular by heat treatment and / or by means of one or more desorption solvents.

[0134] Thus the process of the present invention employs at least one zeolite adsorbent material as indicated above which can be in various forms, and in particular an adsorbent bed, for example one or more types of zeolite in the form of a mixture of crystals or agglomerates, or several identical or different adsorbent beds in the same adsorber, one or more adsorbers being able to be used, in series and / or in parallel, in order to remove as selectively and completely as possible the impurity or impurities present in the composition of organic peroxide.

[0135] More specifically, the process of the invention comprises at least the following steps: a) bringing the organic peroxide composition into contact with at least one zeolitic adsorbent material as defined above, preferably at a temperature between -20°C and +50°C and at atmospheric pressure,

[0136] b) recovery of said organic peroxide, and

[0137] c) optionally regeneration and / or desorption of said at least one zeolitic adsorbent material.

[0138] Preferably, an organic peroxide composition comprising the impurity(ies) at a weight concentration of less than 10%, preferably less than 20%, preferably less than 30%, and preferably even less than 40% by weight relative to the level of impurity(ies) present, in particular alcohol and / or hydroperoxide, in the initial treated liquid (composition comprising the organic peroxide) in step a) is recovered. In other words, the weight removal rate of the impurity(ies) in the composition comprising the organic peroxide(s) is at least 10%, preferably at least 20%, preferably at least 30%, and preferably even less than 40% by weight after step a).

[0139] Preferably, the process according to the invention does not include any step for removing impurities other than by contact with a zeolitic adsorbent material, or preferably does not include any other purification step.

[0140] According to a preferred embodiment, the process of the invention comprises at least one step of contacting a monoperoxycarbonate corresponding to the following formula (I):

[0141] H. A x ..O, ^O"'" YO

[0142] wherein Ri and R2 represent, independently of each other, saturated alkyl radicals, linear or branched, in C2-Ci0; with at least one zeolitic adsorbent material as defined above, preferably at a temperature between -20°C and +50°C and at atmospheric pressure.

[0143] Advantageously, the process according to the invention includes at least one step of contacting OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate with a zeolitic adsorbent material as defined above, preferably at a temperature between -20°C and +50°C and at atmospheric pressure.

[0144] Advantageously, the process according to the invention comprises at least one step of contacting OO-tert-amyl-O-(2-ethylhexyl) monoperoxycarbonate with a zeolitic adsorbent material as defined above, preferably at a temperature between -20°C and +50°C and at atmospheric pressure.

[0145] Composition

[0146] The present invention also relates to an organic peroxide composition comprising a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and more preferably between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals.

[0147] Preferably, the composition of organic peroxide and the zeolitic adsorbent material are as defined above.

[0148] The following examples are intended to illustrate the present invention, but are in no way limiting.

[0149] Chemical analysis of zeolitic adsorbents - Si / Al ratios and metallic cation contents

[0150] An elemental chemical analysis of the zeolitic adsorbent material can be carried out using various analytical techniques known to those skilled in the art. Among these techniques, one can mention the chemical analysis technique by X-ray fluorescence as described in standard NF EN ISO 12677:2011 on a wavelength dispersive X-ray fluorescence (WDXRF) spectrometer, for example the Tiger S 8 from Bruker.

[0151] X-ray fluorescence is a non-destructive spectral technique that exploits the photoluminescence of atoms in the X-ray range to determine the elemental composition of a sample. Excitation of atoms, generally by an X-ray beam or by bombardment with electrons, generates specific radiation after the atom returns to its ground state. The X-ray fluorescence spectrum has the advantage of being largely independent of the chemical composition of the element, thus providing a precise determination, both quantitative and qualitative. After calibration, a measurement uncertainty of less than 0.4% by weight is typically obtained for each oxide. In the present invention, the alkali and alkaline earth metal contents are preferably measured by the X-ray fluorescence method described above.

[0152] On the other hand, for lighter elements in terms of atomic weight such as lithium and sodium, for example, present in the zeolitic adsorbent material, high-frequency induced plasma atomic emission spectrometry (ICP-OES for Inductively Coupled Plasma-Optical Emission Spectroscopy according to the Anglo-Saxon terminology) is preferred for greater accuracy according to the UOP 961-12 standard.

[0153] ICP is an atomic emission spectrometry method whose source is a plasma generated by inductive coupling. In the present invention, sodium content is preferably measured by the ICP method according to UOP 961-12. In this case, the measurement uncertainty for sodium is less than 0.01% for the weight content of sodium oxide in the adsorbent.

[0154] These elemental chemical analyses make it possible both to verify the Si / Al atomic ratio of the zeolite within the agglomerate and to measure the oxide content of alkali and / or alkaline earth metals present in the zeolite adsorbent material according to the invention. In the description of the present invention, the measurement uncertainty of the Si / Al atomic ratio is 5%.

[0155] Loss on ignition of zeolitic adsorbents:

[0156] Loss on ignition is determined in an oxidizing atmosphere by calcining the sample in air at a temperature of 900°C ± 25°C, following the procedure described in standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%.

[0157] Chemical analysis of impurities in the treated peroxide sample

[0158] The sample is analyzed using an Agilent Technologies 7890B GC System instrument equipped with a G4513A type automatic injector, a split / splitless type injector, a flame ionization detector (FID), and a J&W Scientific DB-1 type column, part number 125-1012 (15 m x 530 µm x 1.5 µm). The solvent used for the samples to be analyzed and the standards is HPLC-grade acetonitrile. The limit of detection is 20 ppm and the limit of quantification is 50 ppm. The instrument is calibrated using standards of known purity.

[0159] EXAMPLES

[0160] Preparation of the tested zeolitic adsorbent materials

[0161] LL Zeolitic adsorbent material according to the invention A: LiLSX

[0162] This material is obtained according to the protocol described in application W02018100318 AL

[0163] The material thus obtained is an agglomerate of LSX zeolite crystals, said material being characterized by a molar ratio Si / Al = 1.03 and a molar ratio of sodium oxide (Na2O) to all alkali and / or alkaline earth oxides equal to 0.01.

[0164] L2. Zeolitic adsorbent material according to the invention B: NaKLSX

[0165] The zeolite adsorbent material according to the invention B, is a material obtained according to the operating method described in example 2 of patent EP0932581 B1: it consists of agglomerated LSX zeolite crystals, material not treated with sodium hydroxide (NaOH).

[0166] The material thus obtained is an agglomerate of LSX zeolite crystals, said material being characterized by a molar ratio of Si / Al = 1.04 and a molar ratio of sodium oxide (Na2O) to all alkali and / or alkaline earth oxides equal to 0.77.

[0167] L3. Zeolitic adsorbent material according to the invention C: KY

[0168] The zeolitic adsorbent material according to the invention C is a material obtained according to the operating method described in example 1 of document CN1238238.

[0169] The material thus obtained is an agglomerate of zeolite crystals Y, said material being characterized by a molar ratio Si / Al = 2.73 and a molar ratio of sodium oxide (Na2O) to all alkali and / or alkaline earth oxides equal to 0.05.

[0170] 1.4. Zeolitic adsorbent material according to the invention D: BaX

[0171] The zeolitic adsorbent material according to the invention D is a material obtained according to the operating method described in example 2 of patent EP1864712 B2.

[0172] The material thus obtained is an agglomerate of zeolite crystals X, characterized by a molar ratio Si / Al = 1.25 and a molar ratio of sodium oxide (Na2O) to all alkali and / or alkaline earth oxides equal to 0.03.

[0173] 2, Purification of organic peroxide solutions

[0174] The compositions shown in Table 1 below were tested: [Tables 1] Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Organic peroxide OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate CAS 34443-12-4 OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate CAS 34443-12-4 tert-amyl peroxy-3,5,5-trimethylhexanoate CAS 68860-54-8 tert-butylcumyl peroxide CAS 3457-61-2 l,l-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane CAS 6731-36-8 Purity 98.3% 98.9% 97.1% 94.7% 93.4% Alcohol 1% Ethyl-2-hexanol 0.5% Ethyl-2-hexanol 0.6% 2-methyl-2-butanol / / Hydroperoxide 0.07% Tert-butyl hydroperoxide 0.02% Tert-butyl hydroperoxide 0.1% Tert-amyl hydroperoxide 0.2% Tert-butyl hydroperoxide 0.2% Tert-butyl hydroperoxide Olefin / / / 1.6% α-methylstyrene / Ketone / / / 0.7% Acetophenone 1.8% Trimethylcyclohexanone

[0175] 20 g of composition and 5 g of a zeolitic adsorbent material are placed in a Dig. The environment is agitated.

[0176] Samples are taken after 6 hours of contact using a syringe. The collected mixture is filtered through a PTFE filter with a pore size of 45 µm. The recovered filtrate is analyzed.

[0177] The tests were carried out at ambient temperature and under atmospheric pressure.

[0178] An additional test was carried out at 2°C for Composition 1. Thus, this composition was maintained at 2°C during mixing. This test was carried out under atmospheric pressure.

[0179] 3. Results

[0180] The results (purity, alcohol content, hydroperoxide content) after passing through zeolitic adsorbent material are presented in Table 2 below: [Tables 2] Composition 1 Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 Zeolite adsorbent material used DADCBDBDD Temperature at which the test is carried out Ambient 2°C Ambient Ambient Ambient Ambient Purity 99.49% 98.89% 99.30% 99.27% ​​98.04% 98.11% 95.90% 96.80% 93.94% Alcohol 0.01% Ethyl-2-hexanol 0.47% Ethyl-2-hexanol 0.13% Ethyl-2-hexanol 0.09% Ethyl-2-hexanol 0.02% 2-methyl-2-butanol 0.01% 2-meth yl-2-bu tanol / / Hydrop eroxide 0.01% Tert-bu tyl hyd roperox yde 0.02% Tert-bu tyl hyd roperox yde 0.01% Tert-bu tyl hyd roperox yde 0.01% Tert-bu tyl hyd roperox yde 0.02% Tert-a myl hy dropero oxide 0.01% Tert-a myl hy dropero oxide 0.14% Tert-bu tyl hyd roperox yde 0.08% Tert-bu tyl hyd roperox yde 0.06% Tert-bu tyl hydr operoxy of Oléfin / / / / / 1.27% a-meth ylstyrene 0.58% a-meth ylstyrene / Ketone / / / / / 0.03% 0.01% 1.33% Acetop Acetop Trimeth henone henone yl cyclo hexano ne 4. Conclusions

[0181] These results show that the content of impurities (alcohol, hydroperoxide, ketone, olefin) decreased in the tested samples and that the purity level of the organic peroxide increased. The molecular integrity of the organic peroxides is preserved; they are not degraded by the adsorbent material according to the invention.

[0182] The process remains effective, regardless of the temperature at which the adsorption step takes place.

Claims

Demands

1. Use of a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having an atomic Si / Al ratio between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and preferably still between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals, alone or in mixture to remove at least one impurity, in an organic peroxide composition.

2. Use according to any one of the preceding claims, characterized in that said impurity is selected from the group consisting of one or more alcohols, one or more hydroperoxides, one or more olefins, one or more ketones, one or more acids and mixtures thereof, preferably selected from the group consisting of one or more alcohols, one or more hydroperoxides, one or more olefins, one or more ketones and mixtures thereof, and more preferably one or more alcohols, one or more hydroperoxides and mixtures thereof.

3. Use according to any one of claims 1 or 2, characterized in that the organic peroxide is selected from monoperoxycarbonates, preferably corresponding to the following formula (I): [Chem 3]

4. in which Ri and R2 represent, independently of each other, saturated alkyl radicals, linear or branched, in C2-Ci0. Use according to claim 3, characterized in that the organic peroxide is a monoperoxycarbonate selected from OO-tert-amyl-O-(2-ethylhexyl) monoperoxycarbonate (TAEC), OO-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate (TBEC), OO-tert-octyl-O-(2-ethylhexyl) monoperoxycarbonate (TOEC), OO-tert-hexyl-O-(2-ethylhexyl) monoperoxycarbonate (THEC), tert-amylperoxyisopropyl monocarbonate (TAIC), tert-amylperoxy-n-propyl monocarbonate (TAPC), tert-butylperoxyisopropyl monocarbonate (TBIC), tert-octylperoxyisopropyl propyl monocarbonate (TOIC), tert-hexylperoxyisopropyl monocarbonate (THIC), and mixtures thereof.

5. Use according to any one of the preceding claims, characterized in that the zeolitic adsorbent material is a material in the form of crystals or in the form of agglomerates, preferably in the form of agglomerates, and mixtures thereof.

6. Use according to any one of the preceding claims, characterized in that the zeolitic adsorbent material comprises one or more zeolites selected from zeolites of type LSX, MSX, X and Y, and preferably of type LSX, MSX and X.

7. Use according to any one of the preceding claims, characterized in that said zeolite adsorbent material comprises at least one zeolite selected from the group consisting of: NaKLSX, NaBaLSX, NaLiLSX, LiLSX, BaLSX, BaKLSX, NaCaLSX, CaBaNaLSX, BaX, NaX, NaBaLSX, BaKX, NaCaX, CaBaNaX, BaY, NaKY, BaKY, and mixtures thereof, preferably from the group consisting of NaKLSX, NaBaLSX, NaLiLSX, LiLSX, BaLSX, BaKLSX, NaCaLSX, CaBaNaLSX, BaX, NaBaLSX, BaKX, NaCaX, CaBaNaX, BaY, NaKY, BaKY, and mixtures thereof.

8. Use according to any one of the preceding claims, characterized in that the zeolitic adsorbent material has a loss on ignition of less than 15%, preferably less than 10% and preferably less than 8%.

9. A method for removing one or more impurities from an organic peroxide composition, comprising at least one step of contacting the organic peroxide composition with a zeolitic adsorbent material as defined in any one of the preceding claims.

10. A process according to claim 9, characterized in that the process is carried out in batch, semi-continuous or continuous mode.

11. A method according to claim 9 or 10, characterized in that the contacting step is carried out at a temperature between -20°C and +50°C, preferably between +2°C and +50°C, more preferably between +5°C and +40°C, and at atmospheric pressure.

12. An organic peroxide composition comprising a zeolitic adsorbent material comprising crystals of one or more faujasite-type zeolites, said material having a ratio atomic Si / Al between 1.00 and strictly less than 5.00, preferably between 1.00 and 4.00 and preferably again between 1.00 and 3.00, comprising one or more alkali and / or alkaline earth metals.