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
  • C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to a process for the hydroxylation of phenols and phenol ethers with hydrogen peroxide.
• the invention more particularly relates to a process for hydroxylation of phenol with hydrogen peroxide.
• phenolic substrate is used to designate indifferently a phenol or a phenol ether.
• hydroxylation reaction of phenol with hydrogen peroxide leads to the production of two isomers, namely 1,4-dihydroxybenzene or hydroquinone (HQ) and 1,2-dihydroxybenzene or pyrocatechol (PC).
• HQ hydroquinone
• PC 1,2-dihydroxybenzene or pyrocatechol
• diphenol denotes hydroquinone and pyrocatechol.
• Hydroquinone is a product used in many fields of application as a polymerization inhibitor, an antioxidant in elastomers or as a synthesis intermediate. Another area of application is photography.
• Pyrocatechol is also a widely used product especially as a polymerization inhibitor or antioxidant in elastomers, olefins, polyolefins or polyurethane or as a tanning agent.
• Pyrocatechol because of its complexing properties, is also used as a chelating agent, particularly in the field of electronics and as a corrosion inhibitor.
• Hydroquinone and pyrocatechol are conventionally produced by hydroxylation of phenol with hydrogen peroxide in the presence of an acidic catalyst, strong protonic acid or a solid catalyst with acidic properties, for example TS-1.
• One of the well-known ways of preparing said diphenols is, according to FR 2 071 464, to carry out the hydroxylation of phenol with hydrogen peroxide, in particular presence of a strong protic acid such as, for example, sulfuric acid, chlorosulphuric acid, perchloric acid, sulphonic acids such as, for example, methanesulphonic acid, trifluoromethanesulphonic acid, toluenesulphonic acid, phenolsulphonic acid.
• a strong protic acid such as, for example, sulfuric acid, chlorosulphuric acid, perchloric acid, sulphonic acids such as, for example, methanesulphonic acid, trifluoromethanesulphonic acid, toluenesulphonic acid, phenolsulphonic acid.
• a strong protic acid such as, for example, sulfuric acid, chlorosulphuric acid, perchloric acid, sulphonic acids such as, for example, methanesulphonic acid, tri
• Hydrogen peroxide is used in the form of an aqueous solution.
• the solution of hydrogen peroxide conventionally marketed has a concentration of the order of 30% which induces drawbacks in terms of the reaction because the presence of water slows down the reaction and at the level of the energy balance since this water must then be eliminated.
• US Pat. No. 5,026,925 teaches that the hydroxylation reaction of phenol in the presence of a strong acid, such as, for example, perchloric acid or sulfuric acid, may be improved in particular from the point of view of its yields. In this respect, this patent recommends changing the catalyst, in particular to use sulfur dioxide or selenium.
• No. 5,026,925 still indicates that it is possible to carry out a reaction with an aqueous solution of hydrogen peroxide. However, exemplified aqueous solutions may comprise up to 85% hydrogen peroxide, which is not a commercial grade.
• the phenol is always used in large excess relative to the amount of hydrogen peroxide.
• the molar ratio of hydrogen peroxide / phenol generally ranges from 0.01 to 0.3.
• the phenol conversion rate is kept low (less than 5%) to ensure good reaction performance.
• the conversion rate of the phenol is increased to 15 - 20%, yields of diphenols obtained are halved. Indeed, the yield decreases because the rate of by-products increases by degradation of diphenols in particular, due to consecutive oxidation reactions. It is therefore very interesting to increase the conversion rate of phenol while maintaining the selectivity and / or the yield of hydroquinone and pyrocatechol.
• the object of the present invention is to provide an improved process for the preparation of hydroquinone and pyrocatechol in terms of material balance and energy efficiency.
• the method of the invention is conducted in an apparatus chaining a mixing device in which is made the mixing of the reactants and a piston-flow reactor in which the reaction is conducted.
• the mixing of the reactants is done upstream of the plug flow reactor in a device separate from said plug flow reactor, which makes it possible to increase the safety of the process.
• aqueous solutions of more concentrated hydrogen peroxide whose concentration can vary from 30% to 90% by weight and preferably from 30% to 70%.
• the fact that the introduction of hydrogen peroxide is not made directly at the piston flow reactor provides safety in the event that an incident occurs in the supply of the phenolic substrate.
• the process involves a concentrated solution of hydrogen peroxide and that the introduction of the phenolic substrate would cease there would be accumulation of hydrogen peroxide in the reaction medium and the conditions would then be met for they become explosive.
• the hydroxylation reaction of the phenolic substrate is conducted essentially in the piston-flow reactor which allows a selectivity gain compared to a process where the hydroxylation reaction is conducted in a cascade stirred reactors. Indeed, good selectivity has been achieved due to a limitation of subsequent reactions.
• Another advantage of the process of the invention is that the degree of conversion of the phenolic substrate is increased, for example ranging from 5% to 15%, preferably from 5% to 10%, so that the amount of residual phenolic substrate, to be recycled. is lower which allows to lower the energy consumption.
• Another advantage of the invention is that it leads to a gain in reaction yields.
• Figure 1 is a schematic view of an apparatus adapted to the implementation of the invention.
• the equipment used consists of two sets.
• the first set comprises the reactor (1) equipped with means for introducing the reagents and mixing.
• the second set comprises a piston flow reactor (2).
• mixing the phenolic substrate and the hydrogen peroxide solution is carried out in a mixing device (1); the acid catalyst can be introduced at this reactor and / or at the plug flow reactor.
• the mixing operation is conducted in such a way that the reaction does not begin or begin shortly during this step.
• the degree of conversion of the hydrogen peroxide is less than 25 mol%, preferably between 0.5% and 25% and even more preferably between 0.5% and 15 mol%.
• the temperature of this mixing operation is preferably chosen at most equal to 70 ° C, preferably between 45 ° C and 70 ° C.
• the reaction is conducted essentially in a plug flow reactor (2).
• the temperature in said reactor is higher than that of the mixing device. It is chosen to be greater than 70 ° C., preferably between 75 ° C. and 200 ° C. and more preferably between 75 ° C. and 150 ° C.
• the reactor is a tubular reactor or a column reactor.
• tubular reactor a tube-shaped reactor and “column reactor” a vertical reactor of circular section.
• piston flow is defined a unidirectional flow in which in a plane perpendicular to the flow, all the fluid streams move with a uniform velocity. In such a flow, the radial mixture is perfect while there is no axial mixing. In practice, these conditions are considered fulfilled when the flow is turbulent.
• a flow is turbulent when the Reynolds number is greater than or equal to 5000, and preferentially when it is greater than 10000.
• the radial mixture is not perfect and may be axial backmixing.
• the tubular reactor or column reactor is packed with internals and / or is structured.
• p is the density of the fluid in kg / m 3 ;
• v is the flow rate in m / s
• Re is between 1 and 1,000,000.
• FIG. 2 is a diagrammatic view of an apparatus adapted for implementing a variant of the process of the invention according to which the piston-flow reactor is configured in such a way that the temperature of the reaction is staged.
• FIGS 3 to 5 illustrate types of piston flow reactors that can be used in the method of the invention.
• Figure 3 is a schematic representation of a tubular reactor formed of concentric tubes.
• Figure 4 is a schematic representation of a columnar reactor.
• FIG. 5 schematically represents a multitubular reactor comprising bundled tubes.
• the described process proposes to carry out a hydroxylation reaction of a phenol or a phenol ether.
• the aromatic ring carries at least one hydroxyl group or an ether function.
• the process of the invention is applicable to both phenols and phenol ethers and is also referred to herein as the "phenolic substrate".
• the process of the invention is well suited to the hydroxylation of phenol or of a phenol ether but also to phenols or ethers of substituted phenols.
• phenol or substituted phenol ether is meant a phenol or a phenol ether in which one of the hydrogen atoms of the aromatic ring is replaced by one or more substituents.
• R ⁇ represents a hydrogen atom, an alkyl group, cycloalkyl, aryl, aralkyl,
• R 2 represents a hydrogen atom or one or more substituents, which may be identical or different,
• the number of substituents per aromatic ring is variable and generally less than or equal to 4, preferably equal to 0, 1, 2 or 3.
• n is a number from 0 to 4, preferably equal to 0, 1 or 2,
• R represents a hydrogen atom, an alkyl, cycloalkyl, aryl or aralkyl group
• R 2 which may be identical or different, represent an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom or a halogeno- or perhaloalkyl group.
• n is equal to 0 or 1; represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms; R 2 represents a hydrogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms.
• alkyl means a linear or branched hydrocarbon chain C1-C15, preferably C1-C1 0 and even more preferably CC 4 .
• alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
• alkoxy is meant an alkyl-O- group in which the term alkyl has the meaning given above.
• Preferred examples of alkoxy groups are methoxy or ethoxy.
• cycloalkyl is meant a cyclic, monocyclic C 3 -C 8 hydrocarbon group, preferably a cyclopentyl or cyclohexyl group.
• Aryl means an aromatic mono- or polycyclic group, preferably mono- or bicyclic C6-C2 0, preferably phenyl or naphthyl.
• the group is polycyclic, that is to say that it comprises more than one ring nucleus, the ring nuclei can be condensed two by two or attached two to two by links ⁇ .
• Examples of (C 6 -C 18 ) aryl groups include phenyl, naphthyl.
• aralkyl is meant a linear or branched hydrocarbon-based group carrying a C 7 -C 12 monocyclic aromatic ring, preferably benzyl: the aliphatic chain comprising 1 or 2 carbon atoms
• haloalkyl group means an alkyl group as defined above, one or more hydrogen atoms of which are replaced by a halogen atom, preferably a fluorine atom.
• perhaloalkyl group means an alkyl group comprising from 1 to 10 carbon atoms and from 3 to 21 halogen atoms, preferably fluorine and more particularly the trifluoromethyl group.
• halogen atom is defined fluorine, chlorine and bromine.
• n is equal to 1, such as o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 2-propylphenol, 2- sec-butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, salicylate, methyl, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol,
• n is equal to 2
• phenol, ⁇ -cresol, m-cresol, p-cresol, anisole, phenetole, 2-methoxyphenol (guaiacol), 2-ethoxyphenol are preferably used ( the guetol).
• the present process is particularly suitable for the preparation of hydroquinone and pyrocatechol from phenol.
• an acid catalyst which is a strong acid.
• strong acid is meant in the present invention, an acid having a pKa in water less than - 0.1, and preferably less than -1.0.
• PKa is defined as the ionic dissociation constant of the acid / base pair, when water is used as the solvent.
• acids corresponding to this definition it is preferable to use those which are stable with respect to oxidation by hydrogen peroxide.
• halogenated or non-halogenated oxyacids such as sulfuric acid, phosphoric acid, pyrosulphuric acid and perchloric acid; aliphatic or aromatic sulphonic acids such as, for example, methanesulphonic acid, ethanesulphonic acid, benzenesulphonic acid, toluenesulphonic acids, naphthalenesulphonic acids, benzenedisulphonic acids, naphthalenedisulphonic acids; halosulfonic acids such as fluorosulfonic acid, chlorosulfonic acid, bis-trifluoromethanesulfonimide acid or trifluoromethanesulfonic acid.
• sulfuric acid perchloric acid, methanesulphonic acid, trifluoromethanesulphonic acid, toluenesulphonic acid, phenolsulphonic acid and bis-trifluoromethanesulphonimide acid are preferably used.
• hydroxyaromatic sulphonic acids preferably used in the process of the invention, there may be mentioned the acids corresponding to the following formula:
• x is 1, 2 or 3, preferably 1 or 2
• z is a number from 0 to 4, preferably equal to 0, 1 or 2,
• M represents a hydrogen atom, sodium or potassium
• R represents an alkyl or alkoxy group having from 1 to 4 carbon atoms, a carboxylic group.
• hydroxybenzenesulphonic acids it is preferable to use 4-hydroxybenzenesulphonic acid, 2-hydroxybenzenesulphonic acid, 5-sulphosalicylic acid or a mixture thereof.
• dihydroxybenzenesulfonic acids used include sulfonic acids resulting from the sulfonation of hydroquinone (1,4-dihydroxybenzene), pyrocatechol (1,2-dihydroxybenzene), and resorcinol (1, 3-dihydroxybenzene).
• the preferred dihydroxybenzenedisulphonic acids are 5,6-dihydroxy-1,3-benzenedisulphonic acid, 4,6-dihydroxy-1,3-benzenesulphonic acid, 2,5-dihydroxy-1,4-dihydroxybasic acid and the like. benzenedisulfonic.
• the hydroxyaromatic sulphonic acids are available in solid, liquid or aqueous solution, the concentration of which may vary between 5 and 95% by weight, preferably between 50 and 70% by weight.
• the mixture comprises two acids (A) and (B) respectively having specific pKa: the acid (B) being much stronger than the acid (A).
• Said mixture comprises:
• A a strong acid having a pK a (S) greater than or equal to that of sulfuric acid and a ⁇ 3 (S) with respect to sulfuric acid less than or equal to 4 and greater than or equal to 0
• the acid (A) has a pK a (S) greater than or equal to that of sulfuric acid: (S) representing the organic solvent which is nitrobenzene.
• Acid (B) is a super acid defined as having a pK a (S) lower than that of sulfuric acid.
• PK a (S) is defined as the ionic dissociation constant of the acid / base pair in a solvent (S).
• the pK a of acids is defined by reference to a potentiometric measurement carried out in a solvent which is nitrobenzene (S) and whose measurement protocol is explained before the examples of WO 2010/1 15784.
• the acids involved in said mixture are defined by a difference of pK a , ⁇ pK a which corresponds for the same solvent, the difference between the pK a of the selected acid and pK a sulfuric acid.
• the acid (A) used has a ⁇ 3 (S) with respect to the sulfuric acid of less than or equal to 4 and greater than or equal to 0.
• the acid (A) has a ⁇ 3 (S) with respect to the sulfuric acid of less than or equal to 3 and greater than or equal to 0.
• acids (A) examples include sulfuric acid, aliphatic or aromatic sulphonic acids such as, for example, methanesulphonic acid, ethanesulphonic acid, benzenesulphonic acid, toluenesulphonic acids, naphthalene.
• Another class of acids (A) are hydroxybenzenesulfonic acids, sulfonated hydroxybenzoic acids; hydroxybenzenedisulphonic acids, dihydroxybenzenesulphonic acids, hydroxytoluenesulphonic acids, hydroxynaphthalenesulphonic acids and hydroxynaphthalenedisulphonic acids and mixtures thereof.
• the preferred acids are: 4-hydroxybenzenesulfonic acid, 2-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, sulfonic acids resulting from the sulfonation of hydroquinone (1,4-dihydroxybenzene), pyrocatechol (1,2-dihydroxybenzene) and resorcin (1,3-dihydroxybenzene); 5,6-dihydroxy-1,3-benzenedisulfonic acid, 4,6-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid.
• acids that may be mentioned include perhaloacetic acids such as trichloroacetic acid and trifluoroacetic acid.
• the second component (B) of the acid mixture is a super acid, that is to say an acid having a pK a (S) lower than that of sulfuric acid and which therefore has a negative ⁇ 3 .
• the lower bound is not critical but generally ⁇ 3 in nitrobenzene is less than or equal to - 12.
• the superacids chosen preferentially have a ⁇ 3 less than or equal to -0.1, and preferably greater than or equal to -8.
• superacids (B) examples include perchloric acid, halosulfonic acids such as fluorosulfonic acid, chlorosulfonic acid; perhaloalkanesulfonic acids, preferably trifluoromethanesulphonic acid.
• superacids (B) there may be mentioned inter alia, trifluoromethanesulfinic acid; bis-trifluoromethanesulfonimide acid.
• the proportion in the mixture of different acids can vary widely.
• mixtures comprising:
• Each percentage of acid expresses the ratio (expressed in%) between the number of moles of the acid considered and the number of moles of the sum of the two acids (A) and (B).
• the acids used in the mixture are commercially available in solid, liquid or aqueous solution form whose concentration can vary between 5 and 95% by weight, preferably between 50 and 70% by weight.
• the strong protonic acid or the mixture of acids is used in the process of the invention, in an amount expressed by the ratio of the number of proton equivalents to the number of moles of phenolic substrate which advantageously varies between 0.002 and 0, 15%.
• said molar ratio is preferably selected from 0.01% to 0.07%.
• the hydroxylation of the phenolic substrate is carried out in the presence of a co-catalyst which is a ketone compound and more particularly those corresponding to formula (II):
• R a and R which are identical or different, represent hydrocarbon groups having from 1 to 30 carbon atoms or together form a divalent group, optionally substituted with one or more halogen atoms or stable functional groups under the reaction conditions,
• X represents a valency bond, a group -CO-, a group -CHOH or a group - (R) n -: R representing an alkylene group preferably having 1 to 4 carbon atoms and n is an integer selected from 1 and 16.
• R a and R are more particularly:
• cycloalkyl or cycloalkenyl groups having from 4 to 6 carbon atoms
• R - R a and R may together form an alkylene or alkenylene group having from 3 to 5 carbon atoms, optionally substituted by a lower carbon alkyl group or a cycloalkyl or cycloalkenyl group having 4 to 6 carbon atoms; 2 to 4 carbon atoms of the alkylene or alkenylene groups may be part of one or two benzene rings optionally substituted with 1 to 4 hydroxyl groups and / or alkyl and / or alkoxy low carbon condensation.
• alkyl group of low carbon condensation a linear or branched alkyl group generally having 1 to 4 carbon atoms.
• hydrocarbon groups may be substituted with 1 or more, preferably 1 to 4, low carbon condensation alkyl groups or functional groups such as hydroxyl groups, low carbon alkoxy, hydroxycarbonyl, alkyloxycarbonyl groups having from 1 to 4 carbon atoms. carbon atoms in the alkyl group, a nitrile group, sulfonic group, nitro group or with one or more halogen atoms, and in particular chlorine and bromine groups.
• R a and R are more particularly:
• linear or branched alkyl groups having from 1 to 10 carbon atoms
• linear or branched alkenyl groups having from 2 to 10 carbon atoms
• cycloalkyl or cycloalkenyl groups having from 4 to 6 carbon atoms
• phenyl groups optionally substituted with 1 to 4 alkyl and / or hydroxyl and / or alkoxy groups
• phenylalkyl or phenylacenyl groups containing 1 (or 2) to 10 carbon atoms in the aliphatic part, and even more particularly from 1 (or 2) to 5 carbon atoms in the aliphatic part,
• R and R may together form an alkylene or alkenylene group having from 3 to 5 carbon atoms, optionally substituted by 1 to 4 alkyl groups with a low carbon condensation.
• dialkyl ketone ketone compounds of formula (II) in which R a and R b represent a linear or branched alkyl group having from 1 to 8 carbon atoms are particularly used.
• ketone compounds may be represented by the following formula (IIa):
• R c and R d which are identical or different, represent a hydrogen atom or a substituent, preferably an electron-donating group,
• - nn 2 identical or different is a number equal to 0, 1, 2 or 3,
• the two carbon atoms located at the ⁇ -position with respect to the two carbon atoms bearing the -CO group may be bonded together by a valency bond or by a -CH 2 - group, thus forming a ketone ring which may be saturated but also unsaturated.
• the substituent is chosen such that it does not react under the acid conditions of the invention. It is preferably an electro-donor group.
• electron donor group is meant a group as defined by H. C. BROWN in Jerry MARCH - Advanced Organic Chemistry, Chapter 9, pages 243 and 244 (1985).
• alkoxy groups comprising a linear or branched alkyl chain having from 1 to 4 carbon atoms or a phenoxy group
• ketone compounds having the formula (IIa) in which R c and R d , which are identical or different, represent a hydrogen atom are preferably used; a methyl, ethyl, tert-butyl, phenyl group; a methoxy or ethoxy group; a hydroxyl group, preferably in position 3,3 'or 4,4'.
• ketones that can be used in the process of the invention, there may be mentioned more particularly:
• the amount of ketone compound involved expressed by the ratio between the number of moles of ketone compound and the number of moles of phenolic compound can vary between 0.01% and 20% and preferably between 0.1% and 2%.
• a phenol or a phenol ether is reacted with hydrogen peroxide in the presence of a strong protonic acid and optionally a ketone.
• the hydrogen peroxide used according to the invention may be in the form of an aqueous solution or an organic solution.
• Aqueous solutions being commercially more readily available are preferably used.
• the concentration of the aqueous solution of hydrogen peroxide although not critical in itself, is chosen so as to introduce as little water as possible into the reaction medium.
• An aqueous solution of hydrogen peroxide having an H 2 O 2 concentration of at least 20% by weight and preferably between 20% and 90% by weight is generally used.
• an aqueous solution of hydrogen peroxide having a weight concentration of H 2 0 2 ranging from 30% to 90% and preferably from 30% to 70% is chosen.
• the amount of hydrogen peroxide can be up to 0.5 mole H 2 0 2 per 1 mole of substrate of formula (I).
• water can be brought into the reaction medium including the reagents used.
• an initial content of the water medium of less than 20% by weight and preferably less than 10% by weight.
• the water weight contents indicated are expressed relative to the substrate mixture of formula (I) - hydrogen peroxide - water.
• This initial water corresponds to the water introduced with the reagents and in particular with hydrogen peroxide.
• One variant of the process of the invention consists in adding a complexing agent for the metal ions present in the medium, since these are detrimental to the good progress of the process of the invention, in particular in the case of phenols where the yields of hydroxylation are weak. Therefore, it is preferable to inhibit the action of metal ions.
• the metal ions that are detrimental to the progress of the hydroxylation are transition metal ions and more particularly iron, nickel, copper, chromium, cobalt, manganese and vanadium ions.
• the metal ions are provided by the reagents and in particular the starting substrates and the equipment used. To inhibit the action of these metal ions, it is sufficient to conduct the reaction in the presence of one or more stable complexing agents with respect to hydrogen peroxide and giving complexes that can not be decomposed by the strong acids present and in which the metal can no longer exert chemical activity.
• complexing agents it is possible to use, in particular, the various phosphoric acids such as, for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acids, phosphonic acids such as (1-hydroxyethylidene) diphosphonic acid, phosphonic acid, ethylphosphonic acid, phenylphosphonic acid.
• phosphoric acids such as, for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acids, phosphonic acids such as (1-hydroxyethylidene) diphosphonic acid, phosphonic acid, ethylphosphonic acid, phenylphosphonic acid.
• esters of the abovementioned acids and, more particularly, ortho-phosphates of mono- or di-alkyl, mono- or dicycloalkyl, mono- or dialkylaryl, for example phosphate ethyl or diethyl, hexyl phosphate, cyclohexyl phosphate, benzyl phosphate.
• the amount of complexing agent depends on the content of the reaction medium in metal ions.
• the amount of complexing agents present may be largely in excess of that required to complex the metal ions.
• an amount representing 0.01% and 2%, preferably 0.01 to 0.3% by weight of the reaction medium is suitable.
• the hydroxylation process is generally carried out without any solvent other than that which comes from the reagents, such as the solvent of hydrogen peroxide.
• the reaction can however also be carried out in an organic solvent.
• the solvents used must be stable in the presence of hydrogen peroxide.
• Non-polar solvents such as chlorinated aliphatic hydrocarbons, for example dichloromethane, tetrachloromethane or dichloroethane, may be mentioned.
• polar solvents in particular ethers, for example sulfolane, 1,2-dimethoxyethane, but also acetonitrile, 2-methylglutaronitrile, adiponitrile and dimethylcarbonate.
• FIG. 1 schematizes the steps of the method of the invention without, however, linking the scope of the invention to this one.
• a first step of mixing the reagents carried out in the mixing device (1) is carried out.
• a first class of mixing devices concerns mechanically stirred reactors.
• the reactor is generally of vertical cylindrical shape with flat or elliptical bottom.
• This reactor is equipped with means for introducing the reagents, heating means, a stirring system and in its lower or upper part, a withdrawal system of the reaction mixture.
• the reactor is also provided with a device for measuring temperature and pressure.
• the mixture is conducted in a reactor having good performance in terms of material transfer and heat transfer.
• the stirring system not shown in Figure 1 may be a rotary stirrer.
• stirrers include, among others, the turbine with straight or inclined blades or the marine propeller or any mobile "hydrofoil”.
• a second class of mixing devices relates to external loops.
• the mixture of the reaction medium is then made by loop circulation of a fraction or all of the contents of a stirred reactor mechanically or not, using an external loop pump.
• a third class of mixing devices includes mixers without rotating parts, said dynamic mixers, on the one hand, and static, on the other hand.
• static mixers For so-called static mixers, it is possible to list various internal elements, such as static mixers (Sulzer SMX, Kenics, etc.), a bed of beads or bulk particles, metallic or ceramic foams, etc.
• All of these mixers force the fluid streams fed to exchange the material between them by dividing into sub-nets or creating small scale structures. These structures increase the contact area between the reactant streams.
• the exchange surface to ensure the heat transfer can be increased by coils or plates present inside the reactor or by means of a coolant flowing in a jacket.
• heat-transfer fluids examples include water, water vapor or a suitable organic solvent such as, for example, an aromatic ether such as biphenyl oxide and / or benzyl oxide, a silicone oil, a paraffinic and / or naphthenic oil, petroleum distillation residues, etc.
• a suitable organic solvent such as, for example, an aromatic ether such as biphenyl oxide and / or benzyl oxide, a silicone oil, a paraffinic and / or naphthenic oil, petroleum distillation residues, etc.
• the piston flow reactor has a ratio HSA / equal to or greater than 20 kW / (m 3 .K), and preferably 100 kW / (m 3 .K), and even more preferably between 200 and 20000 kW / (m 3 .K), where H is the overall heat transfer coefficient in W / (m 2 K), S is the heat exchange area (m 2 ), and V represents the reaction volume in m 3 . It is preferred to use a plug flow reactor having an HSA / ratio between 200 and 4000 kW / (m 3 .K).
• reactor-plate exchangers include Alfa-Laval technology as described in patent applications FR2823995, US2004 / 0109798, FR2880967, WO2002 / 08551 1, US2006 / 0159600 and EP1562699, that of Chart and BHR Group with the Marbond TM Hex Reactor reactors, in particular described in WO02 / 37047 and WO02 / 058840, and that of Heatric IP PCR.
• heat-transfer fluids examples include water, water vapor or a suitable organic solvent such as, for example, an aromatic ether such as biphenyl oxide and / or benzyl oxide, a silicone oil, a paraffinic and / or naphthenic oil, petroleum distillation residues, etc.
• a hydrogen peroxide solution (4) is introduced into the mixing device (1), the phenol (3).
• a complexing agent and / or a solvent these may be introduced for example into phenol.
• the catalyst is introduced at (5) or optionally at the top (6) of the plug flow reactor.
• the catalyst can also be introduced in a fractional manner in (5) and
• the various reagents are introduced gradually, preferably continuously: their introduction rate is regulated by means of pump.
• FIG. 1 illustrates the production of the mixture by establishing a recirculation loop as illustrated in FIG.
• Part of the reaction mixture is taken from the bottom of reactor (7) and is then introduced into the reactor in (8): the forced circulation of the mixture being provided by a pump not shown in the diagram.
• the mixing is carried out under conditions such that the reaction is minimized.
• the temperature is chosen such that it is less than or equal to 70 ° C, preferably between 45 ° C and 70 ° C.
• the reaction is advantageously carried out under atmospheric pressure, but higher pressures can also be envisaged. For example, pressures between 5 and 10 bar may be suitable.
• This step can advantageously be carried out under an inert atmosphere, for example under nitrogen or even under argon, nitrogen being preferred especially in view of its reduced cost.
• the residence time and the temperature of the reaction medium in the mixing device must be in adequacy with the degree of conversion of the hydrogen peroxide chosen in said device.
• the reaction mixture then passes from the reactor (1) to the reactor (2) by gravity flow or by forced circulation for example using a pump, usually a centrifugal pump.
• a second step is carried out relative to the hydroxylation reaction conducted in a plug flow reactor (2).
• the reactor consists of a tube (9) inside which circulates the reaction mixture which enters (10) and the products of the reaction which come out in (11).
• the reactor will have a length / diameter ratio greater than 3. It may be in particular a tubular reactor having a length / diameter ratio of between 4 and 30 and in particular between 5 and 10.
• the tubular reactor is formed so as to have a small footprint and increases the piston character, for example when it is folded.
• the reactor material is not particularly limited. It will be chosen so as to be inert under the reaction conditions. Generally, a stainless steel reactor will be selected.
• the tubular reactors are generally arranged horizontally.
• one or more perforated trays are placed near the inlet of the reagents to ensure good homogeneity of the fluids in this section of the reactor.
• the tubular reactor is in the form of a column. It is equipped with reagent inlet ducts and outlet of the reaction mixture.
• the feed of the reagents is carried out by conventional means such as for example a pump and more particularly a centrifugal pump or a volumetric pump.
• the tubular reactor can be equipped with internals.
• the material of the internals does not matter as long as it is chemically inert to the reaction mixture under the conditions of the reaction. Generally, these are materials such as glass, metal, especially stainless steel, carbon, polymer or ceramic.
• the internals are disposed in the reactor near the inlet of the reagents.
• the internals are preferably arranged over the entire height of the reactor. It is then necessary to provide an appropriate support, for example in the form of braces, to maintain the internals in place.
• a static mixer-type packing composed of mixing elements comprising guide blades arranged at precise angles and arranged in a complex manner. This type of packing is for example marketed by SULZER under the name SMV and SMX.
• the Reynolds number is less than 5000, it is possible to implement a reactor without internals and by structuring it.
• After each bend of the tube is introduced a section of internals of equivalent length for example from 3 to 6 times the diameter of the tube, over all or part of the straight length of the tube between two successive bends.
• the appended figures 3 to 5 illustrate the type of equipment that can be used as a piston-flow reactor.
• FIG. 3 represents a tubular reactor formed of concentric tubes.
• the reactor consists of a tube (14) inside which circulates the reaction mixture that enters (19) and the reaction products that come out in (20).
• the heat exchange is provided by a heat transfer fluid, circulating in a double envelope (15), which enters (17) and leaves at (18).
• the tube may contain packing sections after each bend (16).
• FIG. 4 represents a column-shaped reactor (21) equipped with a double jacket (22) or any equivalent means, in which circulates a coolant that enters (23) and exits at (24).
• the column is provided with internals (25).
• the reaction mixture is introduced at (26) and the products stand out at (27). It should be noted that the invention does not exclude the case where the tubular reactor shown in FIG. 5 is of the vertical shell-and-tube shell heat exchanger type.
• the central zone comprises a bundle of parallel tubes (31); each tube having an inlet opening into the inlet zone and an outlet opening into the exit zone.
• the heat transfer fluid entering (32) and exiting at (33) circulates in the shell (36) around the tubes.
• the reaction mixture is introduced at (34) and the products stand out at (35).
• the tubes may or may not be equipped with internals.
• the temperature in said reactor (2) is higher than that of the mixing device. It is chosen to be greater than 70 ° C., preferably between 75 ° C. and 200 ° C. and more preferably between 75 ° C. and 150 ° C.
• the temperature of the hydroxylation reaction is maintained in the above-mentioned temperature range, by regulating the temperature using the means conventionally used for the regulation of temperature and in particular by circulation of a fluid. coolant in the double envelope.
• the reactor is an isothermal reactor.
• Figure 1 represents, for illustrative purposes only, an isothermal reactor.
• the temperature in the reactor is ensured by the circulation of a coolant in a double envelope: the coolant inlet being in (12) and the outlet in (13).
• the reactor is a reaction temperature storage reactor of the reaction medium, with different thermal zones.
• the number of stages may vary for example from 2 to 100, preferably from 2 to 10.
• the temperature in each stage is determined according to the conversion rate of the desired hydrogen peroxide.
• Figure 2 represents, solely for illustrative purposes, a stepped reactor.
• the different temperatures in each stage are ensured by the circulation of a coolant in a double envelope at a different temperature: the coolant inlets in each stage being in (12a), and (12b) and the outputs respectively in (13a) and (13b).
• the temperature range and the residence time of each zone are established in accordance with the reaction performances (conversion rate and yields).
• Staging of the temperature in the process according to the invention can also be carried out in an apparatus consisting of a series of tubular reactors maintained at different temperatures.
• reaction is advantageously carried out under atmospheric pressure but also higher pressures can also be envisaged as previously.
• This step can advantageously be carried out under an inert atmosphere.
• the invention will be explained in more detail by means of examples which illustrate the invention without limiting it.
• the degree of conversion ( ⁇ ⁇ 2 ⁇ 2) of the hydrogen peroxide corresponds to the ratio between the number of moles of hydrogen peroxide converted and the number of moles of hydrogen peroxide introduced.
• the degree of conversion (DC phén0 i) phenol corresponds to the ratio between the number of moles of phenol transformed and the number of moles of introduced phenol.
• the yield of diphenols corresponds to the ratio between the number of moles of diphenols formed (pyrocatechol + hydroquinone) and the number of moles of hydrogen peroxide introduced.
• the yield of pyrocatechol corresponds to the ratio between the number of moles of pyrocatechol formed and the number of moles of introduced hydrogen peroxide.
• the yield of hydroquinone corresponds to the ratio between the number of moles of hydroquinone formed and the number of moles of hydrogen peroxide introduced.
• the selectivity for diphenols corresponds to the ratio between the number of moles of diphenols formed (pyrocatechol + hydroquinone) and the number of moles of hydrogen peroxide converted.
• the ratio PC / HQ is defined by the ratio between the number of moles of pyrocatechol and the number of moles of hydroquinone. Comparative Example 1
• the output rate is adjusted to the incoming flow rate of reagents so as to have a constant reaction volume adjusted to have a passage time of 70 minutes.
• the diphenols formed by high performance liquid chromatography and hydrogen peroxide are titrated by potentiometry.
• Each jacketed reactor is equipped with a mechanical stirring system type 4 inclined blades, a temperature control system, an ascending refrigerant and a nitrogen inlet.
• the outlet flow rate is adjusted to the incoming flow rate of reagents so as to have a constant reaction volume adjusted to have an overall flow time of 70 minutes.
• the reactors are all at the same temperature: 90 ° C.
• the diphenols formed by high performance liquid chromatography and hydrogen peroxide are titrated by potentiometry.
• perchloric acid at a rate of 250 ppm molar to phenol, 2.94 g / h of hydrogen peroxide at 70% by weight (ie 0.0605 mol / h of hydrogen peroxide).
• the passage time in this reactor is 20 minutes.
• Each jacketed reactor is equipped with a mechanical stirring system type 4 inclined blades, a temperature control system, an ascending refrigerant and a nitrogen inlet.
• the output rate is adjusted to the incoming flow rate of reagents so as to have a constant reaction volume adjusted to have a passage time of 67 minutes.
• the reactors are all at the same temperature: 110 ° C.
• the diphenols formed by high performance liquid chromatography and hydrogen peroxide are determined by potentiometry.
• perchloric acid in a proportion of 250 ppm molar to phenol, 6.5 g / h to 70% by weight hydrogen peroxide,
• the passage time in this reactor is 10 minutes.
• the diphenols formed by high performance liquid chromatography and hydrogen peroxide are titrated by potentiometry.
• H 2 0 2 are equivalent whether working in either a cascade of stirred reactors with a phenol conversion of 5%, or with a stirred reactor coupled to a tubular piston reactor with a phenol conversion of about 7%; the operating conditions being equal elsewhere.
• Each jacketed reactor is equipped with a mechanical stirring system type 4 inclined blades, a temperature control system, an ascending refrigerant and a nitrogen inlet.
• the output rate is adjusted to the incoming flow rate of reagents so as to have a constant reaction volume adjusted to have a passage time of 115 minutes.
• the reactors are all at the same temperature: 92 ° C.
• the diphenols formed by high performance liquid chromatography and hydrogen peroxide are titrated by potentiometry.
• the passage time in this reactor is 8 minutes.
• This table shows that the selectivities of diphenols expressed relative to H 2 0 2 are better by conducting the process in the apparatus of the invention comprising a stirred reactor and a tubular reactor operating in piston mode and having a conversion temperature step phenol of the order of 7% only in a cascade of stirred reactors with a phenol conversion of 5% working in isotherm at 92 ° C.
• Example 8 In a reactor of 3 m 3 provided with a jacket and equipped with a stirring system type 4 inclined blades, an ascending condenser, a nitrogen inlet and a temperature control, it introduces at 60 ° C continuously:
• the passage time is 10 minutes.
• a reactor comprising a T-shaped connection serving as a mixer ("T" mixer) connected to a jacketed double-piston reactor made of 316L stainless steel is used.
• T mixer
• a plug flow reactor is described in the application WO 2011/1 17540.
• a valve calibrated at 5 bar absolute at the outlet of the reactor always keeps the reaction medium in the liquid phase.
• the "T” mixer is a standard connection made by Swagelok in 1/16 inch, and is maintained at 50 ° C (electrical resistance).
• the plug flow reactor is a shell-tube type with an internal volume of 7 ml and an internal diameter of 1/8 inch.
• the tubular reactors that were used were tubes of 1/8 inch internal diameters and their length was adjusted according to the residence time. This tube was wound so as to obtain substantially contiguous turns and a compact winding. This winding has been enclosed in an enclosure in which circulates a heat transfer fluid for heating / cooling the tubes. The circulation of the heat transfer fluid and the control of its temperature were ensured thanks to a thermostated bath with circulation.
• the tubular reactor is piston-flowing since it is equivalent to more than 60 reactors perfectly agitated in cascade, for a flow rate between 0.2 and 10 g. min "1.
• the reactor is heated via a silicone oil flow 47V50 to keep a temperature of 165 ° C in the reaction medium.
• the phenol feeds the "T” mixer at a flow rate of 4.8 g. min "1 via a syringe pump heated at 50 ° C, to maintain the liquid phenol.
• the same flow also contains the homogeneous catalyst (perchloric acid hci0 4) at 230 ppm molar, and phosphoric acid a concentration of 200 ppm by weight.
• an aqueous solution of hydrogen peroxide at 70% pP feeds the other mixer bar "T" (in the opposite direction or head to tail) with a flow rate of 12 g. h "1.
• Example 10 In this example, a C276 hastelloy micromixer is used, connected to an enveloped double-jacketed reactor made of 316L stainless steel. A valve calibrated at 5 bar absolute at the outlet of the reactor always keeps the reaction medium in the liquid phase.
• the micromixer was manufactured by the German company IMM under the reference "SuperFocus Interdigital Micromixer SFIMM-V2" and is insulated and maintained at 50 ° C (electrical resistance).
• the piston flow reactor is identical to that of Example 9. This reactor is heated via a 47V50 silicone oil stream in order to maintain a temperature of 165 ° C. in the reaction medium.
• the phenol feeds the micromixer at a rate of 1.2 g. min "1 via a syringe pump heated at 50 ° C, to maintain the liquid phenol.
• the same flow also contains the homogeneous catalyst (HCI04 perchloric acid) at 230 ppm molar, and of a phosphoric acid concentration of 200 ppm by weight
• HCI04 perchloric acid at 230 ppm molar
• a phosphoric acid concentration of 200 ppm by weight
• a 70% aqueous solution of hydrogen peroxide feeds the micromixer separately at a rate of 3 g h -1 .
• the device may comprise a T-shaped connection ("T" mixer) connected to the plate heat exchanger made of 316L stainless steel.
• T T-shaped connection
• the circulation of the heat transfer fluid and the control of its temperature can be assured thanks to a thermostated bath with circulation.
• a valve calibrated at 5 bar absolute at the outlet of the reactor always keeps the reaction medium in the liquid phase.
• the "T” mixer is a standard connection made by Swagelok in 1/8 inch.
• h "1 by a pump head heated and maintained at 50 ° C, to maintain the liquid phenol.
• This same flow can also contain the homogeneous catalyst (perchloric acid HClO 4 ) at a rate of 230 ppm molar, as well as phosphoric acid at a concentration of 200 ppm by mass.
• An aqueous solution of 70% hydrogen peroxide can feed the other mixer bar in "T” countercurrently with a flow rate of 26 g. h "1 , via a pressure syringe.
• Example 11 The same device as for Example 11 can be used with a phenol flow rate of 3.6 kg. h “1 , and with a flow rate of an aqueous solution of hydrogen peroxide at 70% pp of 144 g h -1 , injected separately into the" T "mixer via pressurized piston pumps.

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