Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/14—Adipic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/21—Dicarboxylic acids containing twelve carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
  • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings

Definitions

• the present invention relates to a process for the production of carboxylic acids by oxidation of an alkyl hydroperoxide compound. It relates more particularly to the oxidation of cyclohexyl hydroperoxide to adipic acid by an oxidizing agent containing molecular oxygen.
• adipic acid is an important chemical compound used as a raw material in many manufacturing such as the production of polymers such as polyamides, polyesters or polyurethanes.
• the processes for the manufacture of oxidation of hydrocarbons to dicarboxylic acids by two successive stages of oxidation are used industrially on a large scale. These methods consist, in a first step, in carrying out the oxidation of the hydrocarbons to alcohols and ketones by oxygen or a gas containing oxygen. In a second step, the alcohols and / or ketones are oxidized to acids by nitric oxidation. Different embodiments of these two stages are used.
• the first step can comprise two sub-steps, in a first sub-step the hydrocarbon is oxidized to hydroperoxide. After separation of the hydroperoxide from the unreacted hydrocarbon, the hydroperoxide is decomposed in a separate reactor into alcohol and / or ketone. In another embodiment also used, the production of hydroperoxide and its decomposition into alcohol and / or ketone are carried out simultaneously in a single reactor.
• One of the aims of the present invention is to provide a process for the oxidation of hydrocarbons to produce acids or polyacids, which does not require the use as an oxidizing agent for nitric acid or one of its derivatives and therefore does not produce of nitrogen oxides.
• the invention provides a method of manufacturing carboxylic acids, characterized in that it consists in reacting a hydrocarbon hydroperoxide with oxygen or an oxygen-containing gas in the presence of a catalyst. oxidation comprising a metal belonging to the groups of transition metals.
• the catalyst can advantageously comprise a metallic element chosen from the group comprising Cu, Ag, Au, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Al, Se, In, Tl, Y, Ga, Ti, Zr, Hf , Ge, Sn, Pb, V, Nb, Ta, Cr, Mo, W, Mn, Te, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, lanthanides like Ce and combinations of these.
• These catalytic elements are used either in the form of compounds advantageously at least partially soluble in the liquid oxidation medium under the conditions for carrying out the oxidation reaction, or supported, absorbed or linked to an inert support such as silica , alumina, for example.
• the catalytically active metallic elements are supported or incorporated in a micro or mesoporous mineral matrix or in a polymer matrix or are in the form of organometallic complexes grafted on an organic or mineral support.
• the metal is an element of the support or that one works with complexes sterically trapped in porous structures under the conditions of oxidation.
• the homogeneous or heterogeneous catalyst consists of metal salts or complexes of groups IVb (group of Ti), Vb (group of V), Vlb (group of Cr), Vllb ( Mn group), VIII (Fe or Co or Ni group), Ib (Cu group), and cerium, alone or as a mixture.
• the preferred elements are, in particular, Co and or Mn and / or Cr and / or Zr, Hf, Ce and / or Zr, Hf.
• the metal concentration in the liquid oxidation medium varies between 0.00001 and 5% (% by weight), preferably between 0.0001% and 2%.
• the hydroperoxides which are used in the process of the invention are generally the primary or secondary hydroperoxides derived from alkanes, cycloalkanes, alkyl-aromatic hydrocarbons, the aromatic cycle of which optionally comprises one or more substituents such as in particular an alkyl group or a halogen atom, more particularly a chlorine atom, alkenes and cycloalkenes having from 3 to 20 carbon atoms.
• hydroperoxides examples include cyclohexyl hydroperoxide, cyclododecyl hydroperoxide, tetralin hydroperoxide, ethylbenzene hydroperoxide, pinane hydroperoxide.
• hydroperoxides one of the most interesting is certainly cyclohexyl hydroperoxide, the oxidation of which leads to adipic acid as preponderant dicarboxylic acid, one of the basic compounds for the manufacture of polyamides, more particularly polyhexamethyleneadipate .
• hydroperoxides can be obtained by various processes and used in the process of the invention in purified form or in mixture with other compounds originating in particular from their manufacturing processes.
• the process of the invention can be carried out preferably in the presence of a solvent advantageously consisting of the hydrocarbon used for the manufacture of the hydroperoxide.
• a solvent advantageously consisting of the hydrocarbon used for the manufacture of the hydroperoxide.
• various solvents such as alkanes, among which there may be mentioned more particularly hexane, heptane and isooctane; cycloalkanes among which mention will be made, by way of illustration, of cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons, alcohols, ketones, ethers, ntriles, carboxylic acids such as acetic acid and mixtures of these solvents
• the hydroperoxide is generally produced in the form of a solution in a hydrocarbon, for example cyclohexane, by oxidation of the latter, the oxidation reaction is advantageously carried out on a solution originating from the oxidation of the hydrocarbon (cyclohexane).
• This solution can be used as it is or after elimination of certain constituents in a manner known per se. It is also possible to use a hydroperoxide solution in the solvent, for example, substantially pure cyclohexane.
• the process of the invention can be carried out on a solution originating from the oxidation of a hydrocarbon to hydroperoxide as such or after elimination of certain by-products by, for example, washing the solution with water to eliminate in particular the water-soluble acids or those on the purified hydroperoxide by conventional purification methods such as distillation, extraction or any other conventional method.
• the oxidation reaction is carried out at a temperature between 50 ° C and 250 ° C, preferably between 70 ° C and 200 ° C. It can be carried out at atmospheric pressure. However, it is generally carried out under pressure to maintain the components of the reaction medium in liquid form.
• the pressure can be between 10 KPa (0.1 bar) and 20,000 KPa (200 bar), preferably between 100Kpa (1 bar) and 10,000 Kpa (100 bar).
• the oxygen used can be in pure form or in admixture with an inert gas such as nitrogen or helium. It is also possible to use air more or less enriched with oxygen.
• the oxidation process can be carried out continuously or according to a batch process.
• the liquid reaction medium leaving the reactor is treated according to known methods allowing on the one hand to separate and recover the acids produced and on the other hand to recycle the non-oxidized or partially oxidized organic compounds such as cyclohexane, cyclohexanol and / or cyclohexanone, the catalyst and optionally the solvent.
• the amount of catalyst is generally between 0.00001% and 5% and preferably between 0.0001% and 2%, without these values being critical. However, it is a question of having sufficient activity while not using excessively large amounts of a catalyst which must then be separated from the final reaction mixture and recycled.
• a compound which initiates the oxidation reaction such as for example a ketone, an aldehyde or a hydroperoxide.
• Cyclohexanone which is a reaction intermediate in the case of the oxidation of cyclohexane, is particularly indicated.
• the initiator represents from 0.01% to 20% by weight of the weight of the reaction mixture used, without these proportions having a critical value. The initiator is especially useful when starting the oxidation and when carrying out the oxidation at a temperature below 120 ° C. It can be introduced at the start of the reaction.
• reaction medium another compound which may in particular have the effect of improving the productivity and / or the selectivity of the acid oxidation reaction adipic, such as improving the solubilization of oxygen.
• nitriles such as acetonitrile, benzonitrile, halogenated derivatives such as dichloromethane, fluorinated compounds such as:
• fluorinated aliphatic hydrocarbons or perfluorinated cyclic or acyclic, aromatic fluorinated hydrocarbons such as perfluorotoluene, perfluoromethylcyclohexane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecalin, perfluoromethyldecalin, ⁇ , ⁇ , ⁇ -trifluorotoluene, 1, 3-bis (methyl trifluoropropyl) benzene.
• Fluorinated or perfluorinated acids such as trifluoromethyl benzoic acids, pentafluorobenzoic acid, hexanoic, heptanoic, octanoic, nonanoic acid, perfluorinated adipic acid, perfluorinated
• Fluorinated or perfluorinated amines such as perfluorinated tripropylamine, perfluorinated tributylamine, perfluorinated tripentylamine - Carboxylic acids such as valeric, glutaric, succinic acids; derivatives of aminocaproic acid, acids of lipophilic nature such as tertiobutyl benzoic acid.
• lipophilic carboxylic acids suitable for the invention mention may be made of hexanoic, heptanoic, octanoic, 2-ethylhexanoic, nonanoic, decanoic, undecanoic, dodecanoic, stearic (octadecanoic) acids and their permethylated derivatives (total substitution of hydrogen for methylene groups by methyl group), 2-octadecylsuccinic acid, 2,5-ditertiobutyl benzoic acid, 4-tertiobutylbenzoic acid, 4-octylbenzoic acid, tertiary butyl hydrogen orthophthalate, naphthenic or anthracene acids substituted by alkyl groups, preferably of the tertiobutyl type, substituted derivatives of phthalic acids, fatty diacids such as the fatty acid dimer. Mention may also be made of acids belonging to the preceding families and carrying different electron donor
• the reaction mixture resulting from the oxidation is subjected to various operations of separation of some of its constituents to, for example, allow their recycling at the level of oxidation and the recovery of the acids produced.
• the crude reaction mixture can firstly be subjected to cooling to a temperature of 16 ° C to 30 ° C for example, which causes the crystallization of at least part of the acid form.
• a medium comprising a solid phase consisting essentially of acids, at least one organic liquid phase containing essentially the unreacted compound to be oxidized, optionally the solvent and the oxidation intermediates or other products resulting from the oxidation , and an aqueous liquid phase containing essentially acid byproducts of oxidation and the water formed.
• the catalyst can be in one of the organic phases if it is soluble in said phase, or in the lower aqueous phase.
• the organic and aqueous liquid phases constituting the filtrate or the centrifugate are separated, if necessary, by decantation: the organic phase or phases can be recycled in a new oxidation reaction.
• the final raw reaction mixture can be drawn off hot, for example at a temperature which can reach 75 ° C.
• the reaction mixture then settles into at least two liquid phases: one or more organic phases containing essentially the unreacted hydrocarbon, the solvent, oxidation intermediates and an aqueous liquid phase containing essentially the acids formed and the water formed.
• the catalyst can be present in the organic phase (s), recovered by solid / liquid separation before precipitation or crystallization of the acid formed in the case of heterogeneous catalysis or if it is soluble in the aqueous phase, extracted by liquid / liquid extraction, on resin or electrodialysis.
• the liquid phases are separated: the organic phase or phases can be recycled in a new oxidation reaction.
• water can be added to the reaction medium to obtain better dissolution of the acid byproducts of the oxidation and better recovery of the acid formed.
• the acid is generally recovered by precipitation during the cooling of the reaction medium.
• the acid thus recovered can be purified according to usual techniques and described in numerous patents. By way of example, mention may be made of French patents Nos. 2749299 and 2749300.
• the non-organic or aqueous liquid phase contains the catalyst, it is extracted either before the crystallization of the acid formed by precipitation or extraction according to known methods such as liquid-liquid extraction, electrodialysis, treatment on exchange resins d ions for example, either after crystallization of the acid formed by extraction techniques described above or the like.
• the invention also relates to a process for the manufacture of carboxylic acids consisting in a first step of oxidizing a hydrocarbon to hydroperoxide with oxygen or an oxygen-containing gas.
• the medium obtained, after optional concentration by evaporation of part of the unreacted hydrocarbon, is subjected to a second stage of oxidation of the hydroperoxide to carboxylic acids in accordance with the process of the invention described above .
• the reaction medium resulting from the first oxidation step is subjected to various separation and elimination treatments of by-products to purify the hydroperoxide. These treatments may include washing the oxidation medium with water or a slightly basic solution.
• Cyclohexanone 2.06% The autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven. The mixture is heated to 130 ° C, with shaking.
• TT we mean the transformation rate of the product calculated by the ratio between the difference between the number of initial molecules and the number of final molecules compared to the number of molecules initials.
• HPOCH - cyclohexyl hydroperoxide
• the autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven. The mixture is heated to 130 ° C, with shaking. After 180 minutes of reaction, the autoclave is cooled and then degassed. The reaction mass collected is analyzed by gas chromatography (GC). The following results were obtained:
• Example 3 7.6 mg of ScCI 3 , 6 H 2 O and 4.56 g of a cyclohexyl hydroperoxide solution from the oxidation of cyclohexane, to the following composition, are loaded into a 30 ml Hastelloy C22 autoclave. expressed in mass% for the main components: - cyclohexyl hydroperoxide (HPOCH) 10.93%
• the autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven.
• the mixture is heated to 130 ° C, with shaking.
• Adipic acid 105 mg
• the autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven. The mixture is heated to 130 ° C, with shaking. After 180 minutes of reaction, the autoclave is cooled and then degassed. The reaction mass collected is analyzed by gas chromatography (GC). The following results were obtained:
• Example 5 3 mg of Mn acetylacetonate (III), 142 mg of valeric acid and 4.57 g of a cyclohexyl hydroperoxide solution from the oxidation of cyclohexane are charged into a 30 ml Hastelloy C22 autoclave. washed with water, with the following composition expressed in% by mass for the main components: - cyclohexyl hydroperoxide (HPOCH) 9.85%
• the autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven. The mixture is heated to 130 ° C, with shaking. After 180 minutes of reaction, the autoclave is cooled and then degassed. The reaction mass collected is analyzed by gas chromatography (GC). The following results were obtained:
• HPOCH - cyclohexyl hydroperoxide
• the autoclave is immediately pressurized to 100 bar of air at room temperature and placed in an oven. The mixture is heated to 130 ° C, with shaking. After 180 minutes of reaction, the autoclave is cooled and then degassed. The reaction mass collected is analyzed by gas chromatography (GC). The following results were obtained:
• Example 7 32 mg of Mn acetylacetonate (III) and 41.4 g of a cyclohexyl hydroperoxide solution from the oxidation of cyclohexane, to the following composition, expressed in%, are charged into a 180 ml titanium autoclave. mass for the main components: - cyclohexyl hydroperoxide (HPOCH) 10.76%
• the autoclave is immediately pressurized to 75 bar of air at room temperature.
• the reactor is then heated to 130 ° C. and then connected to an oxygen reserve ensuring, during the reaction time, a partial oxygen pressure of 20 bar for a total pressure of the autoclave of 100 bar.
• the whole is subjected throughout the duration of the reaction to stirring at 1000 revolutions per minute.
• the autoclave is immediately pressurized to 75 bar of air at room temperature.
• the reactor is then heated to 130 ° C. and then connected to an oxygen reserve ensuring during the reaction time a partial oxygen pressure of 20 bar for a total autoclave pressure of 100 bar.
• the whole is subjected throughout the duration of the reaction to stirring at 1000 revolutions per minute.

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• 2002
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