Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides

Definitions

• the present invention relates to the use of alkanesulfonic acid for the preparation of phenolic alcohol.
• the invention also relates to a process for the preparation of phenolic alcohol by decomposition of aryl hydroperoxide.
• the strong acids usually used are sulfuric acid, hydrochloric acid or phosphoric acid which generate, after neutralization of the reaction medium with an aqueous base, sulphates, chlorides or phosphates.
• Each of these acids has disadvantages, in terms of corrosion, or generation of effluents harmful to the environment, to name only some of these disadvantages.
• insoluble compounds in the streams of an industrial distillation plant is highly detrimental in that these insoluble compounds can cause flow disturbances, especially in the distillation column itself, and consequently lead to losses of load, even risk of co-slagging, deposits, etc.
• any loss of charge requires greater energy consumption, in particular to operate at a higher temperature, which results in degradations and decompositions of the products, thus causing a loss of quality of the purified phenol and losses of overall distillation yield.
• the inventors have found that the use of one or more alkanesulphonic acids leads to a clear improvement of the phenol preparation process.
• the alkanesulfonic acid is not desiccant. Indeed, in the case of the phenol synthesis, it has been observed that the content of by-products, especially acetone, such as mesityl oxide is lower. As a result, a gain in selectivity and yield is observed.
• the neutralization of the reaction medium results in the formation of insoluble salts, such as sodium or potassium sulphates, which need to be removed generally by filtration, before carrying out the distillation.
• insoluble salts such as sodium or potassium sulphates
• the use of alkanesulfonic acid has the advantage of leading to the formation of organic salts which are more soluble in the reaction medium. As a result, the filtration step becomes unnecessary. In addition, the risks of clogging due to the presence of salts are avoided. Therefore, on the industrial level, the use of alkanesulfonic acid allows a gain in productivity by simplifying the process.
• a first object of the present invention is the use of at least one alkane-sulfonic acid for the preparation of phenolic alcohol by decomposition of aryl hydroperoxide and preferably the use of at least one acid alkanesulfonic acid for the preparation of phenolic alcohol and ketone or aldehyde by decomposition of aryl hydroperoxide.
• Another object is to provide an improved process for the preparation of phenolic alcohol comprising a step of decomposing aryl hydroperoxide in the presence of at least one alkane sulfonic acid.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., bounds a and b excluded), while any range of values designated by the expression “from a to b” means the range of values from a to b (c) that is, including terminals a and b).
• the present invention relates to the use of at least one alkanesulfonic acid for the preparation of phenolic alcohol by decomposition of aryl hydroperoxide.
• aryl hydroperoxides are understood to mean compounds with aromatic groups whose hydroperoxide function is carried by a carbon atom positioned in the alpha position of the aromatic ring.
• Aromatic means aromatic rings having from 6 to 14 carbon atoms, preferably from 6 to 10 carbon atoms (inclusive) and typically phenyl and naphthyl.
• aryl hydroperoxides according to the present invention are preferably of the following general formula (or structure) (I):
• the groups R 1 and R 2 denote, independently of one another, a hydrogen atom, a C 1 to C 18 , preferably C 1 to C 10 , more preferably C 1 to C 6 , linear alkyl radical; or branched, a C 6 to C 14 aryl radical, preferably a C 6 to C 10 aryl radical, and typically phenyl and naphthyl,
• the groups R 3 to R 7 denote, independently of one another, a hydrogen atom, a C 1 -C 18 alkyl radical, preferably Ci -C 10, more preferably C, to C 6 linear or branched, a halogen atom, in particular fluorine, chlorine, bromine and iodine, a radical -N0 2, -CN radical, a substituted alkyl radical by one or more halogen atoms, a C 6 to C 12 aryl radical,
• R 3 to R 7 may together form one or more aliphatic or aromatic rings.
• R 3 and R 4 may together form an aromatic ring of 6 carbon atoms then leading to a naphthalene hydroperoxide.
• R 3 and R 4 can also together form an aromatic bicycle with 12 carbon atoms, thus leading to an anthracene hydroperoxide.
• the groups R 1 and R 2 are chosen from a hydrogen atom, a methyl, an ethyl, an n-propyl, an iso-propyl, a n-butyl, an isobutyl or a tert-butyl.
• the groups R 3 to R 7 are chosen from a hydrogen atom, a methyl, an ethyl, an n-propyl, an iso-propyl, an n-butyl, an isobutyl or a tert-butyl, a chlorine atom, a fluorine atom, a bromine atom, a phenyl radical.
• the group R 1 in the compound of formula (I) does not represent the hydrogen atom.
• the group R 2 in the compound of formula (I) does not represent the hydrogen atom.
• the groups R 1 and R 2 in the compound of formula (I) do not denote a hydrogen atom.
• the aryl hydroperoxide is chosen from cumyl hydroperoxide, butylbenzene hydroperoxide, ethylisopropylbenzene hydroperoxide, (propyl) naphthalene hydroperoxide, diisopropylbenzene hydroperoxide and hydroperoxide.
• sec-butylbenzene hydroperoxide, para-ethyl-iso-propylbenzene hydroperoxide and ⁇ -z 'so-propylnaphtalène preferably cumyl hydroperoxide.
• phenolic alcohol is meant in the sense of the present invention phenol and phenols bearing substituents R 3 to R 7 .
• R 1 is hereinafter referred to as the co-product. It can be a ketone or an aldehyde according to whether R 1 and / or R 2 represent (nt) a hydrogen atom.
• cumyl hydroperoxide is used. S decomposition in acidic medium leads to the formation of phenol and acetone.
• the decomposition of aryl hydroperoxide into alcohols is most often carried out in an acid medium, or at least in the presence of acid (s), and preferably in the presence of an aqueous solution of at least an alkanesulfonic acid.
• alkanesulfonic acid means the acids of the following general formula (II):
• group R represents a saturated or unsaturated hydrocarbon chain, linear or branched having from 1 to 6 and preferably from 1 to 4 carbon atoms.
• R represents a saturated, linear or branched hydrocarbon-based chain containing from 1 to 6 and preferably from 1 to 4 carbon atoms are preferred.
• alkane-sulphonic acids that can be used in the context of the present invention are very particularly preferred. selected from methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, isopropane sulfonic acid, n-butanesulfonic acid, iso-butane sulphonic acid, sec-butanesulfonic acid, tert-butanesulphonic acid, and mixtures of two or more of them in all proportions.
• the pKa of the alkanesulfonic acids are all less than zero.
• any type of formulation comprising at least one alkanesulfonic acid may be suitable. It is possible to use at least one alkanesulphonic acid in anhydrous form or in the form of an aqueous solution.
• the formulation comprises from 1% to 100% by weight of alkane-sulphonic acid (s), preferably from 1% to 99% by weight, more preferably from 1% to 95% by weight, in general. from 5% to 95% by weight and more generally from 5% to 90% by weight, in particular from 10% to 80% by weight of alkanesulphonic acid, and more particularly from 15% to 75% by weight, 100% supplement usually consisting of water.
• the formulation comprises 100% by weight of alkane-sulphonic acid (s)
• the alkane-sulphonic acid (s) are used pure, more precisely are used alone, without addition of other formulation components.
• the formulation also comprises the possible presence of one or more additives well known to those skilled in the art and by way of nonlimiting examples chosen from solvents, hydrotropic or solubilizing agents, biocides, disinfectants, rheological agents, preservatives, surfactants and the like.
• additives well known to those skilled in the art and by way of nonlimiting examples chosen from solvents, hydrotropic or solubilizing agents, biocides, disinfectants, rheological agents, preservatives, surfactants and the like.
• active ingredients organic or inorganic acids (eg sulfuric, phosphoric, nitric, sulfamic, acetic, citric, formic, acetic, glycolic, oxalic and others), foaming agents, antifoam agents, anti-gels (for example ethylene glycol, propylene glycol, and the like) ), dyes, perfumes, anti-corrosion additives, UV protectors and other additives known to those skilled in the art, alone or as a mixture of two or more of them in all proportions.
• organic or inorganic acids eg sulfuric, phosphoric, nitric, sulfamic, acetic, citric, formic, acetic, glycolic, oxalic and others
• foaming agents for example ethylene glycol, propylene glycol, and the like
• antifoam agents for example ethylene glycol, propylene glycol, and the like
• dyes for example ethylene glycol, propylene glycol, and the like
• the formulation is for example an aqueous formulation which can be prepared as a concentrated mixture which is diluted by the end user.
• the formulation may also be a ready-to-use formulation, i.e., it does not need to be diluted.
• methanesulphonic acid in aqueous solution sold by Arkema, for example an aqueous solution of methanesulphonic acid at 70% by weight in water, or even methanesulphonic acid.
• Anhydrous sulfonic acid or AMSA acronym for "anhydrous methane sulphonic acid" in English.
• the present invention relates to the use, for the preparation of phenol by decomposition of cumyl hydroperoxide in the presence of methanesulfonic acid (AMS) in all possible concentrations, ranging from AMSA ( AMS anhydrous) at concentrations of the order of 5% by weight of AMS in water, and in particular the aqueous solutions of AMS at 70% by weight in water, marketed by the company ARKEMA.
• AMSA AMS anhydrous
• alkanesulfonic acid or a mixture of alkanesulfonic acids alone.
• the invention also relates to a process for preparing phenolic alcohol, comprising a step of decomposing aryl hydroperoxide in the presence of alkanesulfonic acid.
• the method according to the invention comprises the following steps:
• the reagent of the process according to the invention is aryl hydroperoxide, as described above and more particularly cumyl hydroperoxide.
• the reaction crude of the hydroperoxidation step may comprise benzene derivatives, such as cumene, dimethylphenylcarbinol, dicumyl, dicumyl peroxide, acetophenone.
• the acidic catalyst comprises at least one alkanesulfonic acid as described above and advantageously methanesulfonic acid. It can be used pure or in aqueous solution.
• the content of alkane-sulphonic acid (s) is between 100 ppm and 50,000 ppm, more particularly between 200 and 8,000 ppm, relative to the aryl peroxide (s) introduced. .
• the amount of alkane-sulphonic acid (s) introduced into the reaction crude may therefore vary according to the reagent present, namely the pure aryl hydroperoxide or the reaction crude of the hydroperoxidation. Those skilled in the art will be able to adapt the amount of alkane-sulphonic acid (s) to be added to the reaction crude depending also on the concentration of said acid (s).
• the acid is introduced either into the stream of the aryl hydroperoxide or into the stream of solvent, which solvent is generally added as a diluent because the reaction is very exothermic. This reaction is generally, and most often, carried out in the liquid phase.
• the reaction solvent may be any organic solvent or mixture of organic solvents, optionally with water (hydro-organic solvents) known to those skilled in the art and suitable for this type of reaction, and in particular one or more solvents ( s) organic (s) polar (s), protic (s) or aprotic (s), preferably polar (s) and aprotic (s).
• solvents s
• protic (s) or aprotic (s) preferably polar (s) and aprotic (s).
• Ketones and especially acetone (dimethylketone), are particularly suitable for carrying out the process according to the present invention.
• the reaction temperature is generally between
• the aryl hydroperoxide, pure or in the crude reaction is reacted, optionally but preferably in a solvent medium, with at least one alkanesulfonic acid, as described above.
• the process then comprises a step of neutralizing the reaction medium.
• the neutralization of the acid phase is not without consequences on the nature of the medium which is intended to be distilled. Indeed, during this neutralization step, the acidic species are neutralized in the form of salts.
• the inventors have surprisingly discovered that the different alkali metal and / or alkaline earth metal salts, present in this phase, thus neutralized and intended to be distilled, are more soluble in the phenol / ketone / water or phenol mixture.
• water when the neutralization has been carried out on a medium previously acidified with at least one alkanesulfonic acid, in particular methanesulphonic acid, whereas the same salts are less soluble when the acidification has It has been carried out with other acids, especially strong mineral acids commonly used in the field, such as sulfuric, hydrochloric or phosphoric acids.
• alkanesulfonates preferably methanesulfonates
• sulphates chlorides and other phosphates in the phenol / ketone mixture. (or aldehyde) / water or phenol / water (once ketone or distilled aldehyde).
• distillation operations are very sensitive to solid impurities present in the distillation plants and in particular in the distillation boiler (or foot) but also in the distillation columns.
• phenol / ketone / water (or phenol / water) concentration gradients and temperatures vary along the distillation columns.
• Acidification with at least one alkanesulphonic acid, and preferably with methanesulfonic acid has the advantage of improving the solubility of the salts, especially the sodium and / or potassium salts present in the phenol mixture. / ketone / water (or phenol / water).
• this greater solubility of the salts of alkanesulfonic acids in the phase comprising phenol, and in particular in the boiler, at the bottom of the column makes it possible to continue the distillation operation to a more advanced degree. , and thus further improve the distillation yield.
• Another advantage related to a better solubility of the salts in the phenol is the reduction of the risk of coagulation in the bottom of the column, where the phenol / water mixtures are the most concentrated in phenol. The overall yield of the distillation is thus greatly improved.
• the greater solubility of the salts in the medium to be distilled can also make it possible to envisage a significant reduction in the number of theoretical plates of the column, and consequently the physical height of the column, as well as substantially reducing the quantity of column. energy used for the total distillation of phenolic alcohol.
• Yet another advantage, related to the acidification by at least one alkanesulphonic acid of the crude reaction containing the phenolic alcohol, is that the solids deposits are less important and therefore the shutdown periods for cleaning. Distillation plants are further spaced over time.
• alkanesulfonates and more particularly the methanesulfonates, are very soluble in an aqueous medium and are biodegradable.
• the installations are therefore easier to clean, and as a result require much smaller volumes of water, and the cleaning effluents are more respectful of the environment.
• the bases used are mineral species which are inert with respect to the species present in the reaction medium. More particularly, the bases are selected from alkali metal or alkaline earth metal hydroxides, such as sodium or potassium hydroxide, alkali metal or alkaline earth metal carbonates. These bases are most often and advantageously used in aqueous solution. Preferably, sodium hydroxide is used.
• insoluble salts are present, a filtration step may be contemplated, although this is not a preferred variant of the process of the invention.
• insolubles can in particular come from the hydroperoxidation reaction crude.
• a settling step is carried out in order to separate the aqueous phase from the neutralization solution and the organic phase containing the species to be purified.
• the phenolic alcohol present in the neutralized reaction medium is then separated from the residual water and by-product.
• This separation can be carried out according to any method known to those skilled in the art and, preferably, by distillation. During this distillation operation, the co-product is first distilled, then water, and finally phenolic alcohol.
• the distillation of the phenolic alcohol is generally carried out under reduced pressure, generally under vacuum (for example at 280 mm Hg, 37.33 kPa) with boiler at 170 ° C. and distillation of the phenol at about 150 ° C.
• This process is characterized in that it uses at least one alkanesulfonic acid and more preferably methanesulfonic acid.
• This acid has the advantage of being less corrosive, biodegradable, respectful of the environment, and also has the advantage of solubilizing the salts present in the reaction medium allowing the conduct of the final distillation of the acid. phenolic alcohol under more economical conditions, as explained above in the description.
• the method according to the invention comprises the following steps:
• the solubility is calculated as follows:
• % solubility salt m / (m + M) x 100
• a first measurement is made at 20 ° C at atmospheric pressure, then a second measurement is performed at 60 ° C.
• the point at 60 ° C makes it possible to evaluate the solubility of the species in the boiler during the distillation of acetone.
• potassium methanesulfonate is more than 6.7 times more soluble than potassium sulfate.
• a first measurement is performed at 55 ° C at atmospheric pressure, then a second measurement is performed at 100 ° C.
• the point at 100 ° C makes it possible to evaluate the solubility of the species in the boiler during the distillation of the water.
• potassium methanesulfonate is respectively 15 and 8 times more soluble than potassium sulfate.
• sodium methanesulfonate is more than 2 times more soluble than sodium sulfate.

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• 2014
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