Classifications

• • 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
  • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
  • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Definitions

• the present invention relates to a catalytic system for the hydroformylation of olefins also called the OXO reaction. It also relates to the hydroformylation process from the catalytic system.
• the processes for hydroformylation of an olefin to prepare aldehydes or alcohols having a carbon atom more than the initial olefin consist in reacting this olefin with a synthesis gas in the presence of a complex catalyst containing a chosen metal in the transition metals series.
• the metals of group VIII of the periodic table that is to say iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, are particularly used.
• metals can be used in the form of carbonyl metals, but it is recognized that complex combinations containing, in addition to the metal and carbon monoxide, at least one biphyllic ligand such as a phosphine, lead to more linear products and allow to work at low synthesis gas pressures. Such combinations are, for example, described in French Patent No. 1,300,404 or even in United States Patent No. 3,239,566.
• conjugated dienes are designated molecules having in their structures the motif - or the reason . These motifs can belong to aliphatic, alicyclic, heterocyclic or aromatic molecules.
• the compounds whose molecules can generate in situ during the hydroformylation reaction a structure such as those described above; by way of example, this is the case for ⁇ -diketones or quinones which, through the play of automeric or chemical equilibria, generate conjugated dienes.
• the diene can also be introduced in the form of a complex combination with one of the two metals falling within the scope of the invention, for example in the form of cobalt dicarbonyl cyclopentadienyl or cobalt acetylacetonate.
• the cobalt / diene ratio is fixed; to obtain a different ratio it may be necessary to add additional diene which, moreover, may be different from the combined diene.
• the rhodium compound is a complex combination of rhodium, carbon monoxide and tri ⁇ rganophosphorus ligand.
• the use of such combinations taken in isolation as an OX0 catalyst is known.
• the triorganophosphorus ligand is chosen from arylphosphines or arylphosphites.
• An example of such a combination when the ligand is Ira triphenylphosphine, is rhodium (I) hydrogenocarbonyl tris (triphenylphosphine) of formula H Rh CO
• Cobalt can be efficiently introduced into the reaction medium in a wide variety of forms. Most combinations containing cobalt can be used. One can for example introduce cobalt in a carbonylated form such as Co 2 (CO) 8 or H Co (CO) 4 ; cobalt can also be used in the form of a mineral salt or an organic salt such as cobalt acetate, cobalt acetylacetonate, b ⁇ nzoate or cobalt naphtenate. Obviously the cobalt compound used must not contain a group capable of being a poison for the OXO reaction itself; it is known that the chloride or sulphide ions are poisons for the OX0 synthesis. Such compounds are cited in particular in the book by J.
• the triorganophosphorus compound is chosen from arylphosphines or arylphosphites; it is not necessarily of the same nature as the organophosphorus ligand introduced with rhodium, but when this is the case, it can then be considered as an excess of this ligand in the reaction medium.
• the rhodium concentrations can be between 10 - 4 and 10 - 1 mole / liter of reaction solution, but satisfactory results are obtained for concentrations between 10 -3 and 10 -2 mole / liter.
• the amounts of cobalt can be introduced at concentrations of between 10 - 4 and 1 mole / liter of reaction solution.
• concentrations of between 10 - 4 and 1 mole / liter of reaction solution When using high cobalt concentrations, precipitates can be observed in some cases due to the limited solubility of organometallic complexes in the reaction medium. This solubility obviously depends on the solvent medium. If it is desired to avoid such precipitates, it will be necessary to determine the cobalt concentrations allowing the solubility limits not to be exceeded. In practice, we will generally operate at concentrations of between 2X10 - 4 and 0.2 mole / liter. The diene concentration is between 5 ⁇ 10 -3 and 350 g / liter of reaction solution. Good results are generally obtained for concentrations of between 5 ⁇ 10 -2 and 200 g / liter.
• the properties of the diene such as for example the steric hindrance or the electronic factors influence the stability of the complexes involved in the catalytic process and that consequently the concentrations of diene for which the catalytic system is particularly effective could vary d from one diene to another.
• the diene concentration ranges mentioned above are given for information and are generally suitable for the majority of dienes; the specialist will be able, after a few conventional tests, to select the most appropriate values in this field, that is to say values which do not lead to a slowing down of the reaction.
• Organophosphorus ligands such as arylphosphines or arylphosphites are used in phosphorus / rhodium molar ratios greater than 10.
• the hydroformylation of olefins with the present catalytic system is generally carried out at a temperature between, approximately 60 ° C and approximately 150 ° C, temperatures between 80 ° C and 125 ° C being most often used, the pressure fairly low total of hydrogen and carbon monoxide being between 1 and 40 bars approximately and the H 2 / CO molar ratio comprised between approximately 1/1 and 20/1.
• the process can be implemented by having a feed stream comprising a mixture of hydrogen and carbon monoxide, the olefinic feedstock to be hydroformylated and new or recycled catalyst dissolved in a reaction zone. solvent or in the heavy products of the reaction.
• the reaction product can be recovered from the reaction medium by distillation of a liquid stream withdrawn continuously from the reactor, the heavy products containing the catalyst being optionally recycled as already mentioned.
• the reaction products can also be recovered by extracting them directly from the reaction medium by entrainment in a gas stream leaving the reaction zone, which can be, for example, excess syngas.
• This process has the advantage of leaving the catalytic system in place but it is conveniently only applicable for the hydroformylation of light olefins such as propene, butenes or pentenes.
• the complexes are introduced from the start to obtain a substantial gain in activity compared to known catalysts.
• EXAMPLE 1 In general, the following tests 1 to 19 are carried out in a 200 ml stainless steel autoclave equipped with an agitator, a temperature measurement and a pipe intended for the gas supply. 20 ml of n-butanal, 43 mg of hydridocarbonyl tristriphenylphosphine rhodium (H Rh C0 (P ⁇ 3 ) 3 ) and 1.33 g of triphenylphosphine P ⁇ 3 are introduced . The cobalt and the diene are then added in the proportions described in Table 1. After closing the autoclave and starting stirring, the autoclave is heated to reach a temperature of 95 ° C; the relative pressure is then 1.8 bar.
• Tests 1 to 4 are given for comparison.
• Tests 1 and 2 illustrate the harmful effect of the dienes on conventional catalysts. They show that the addition of a diene to a catalytic system consisting of a rhodium complex and a phosphine or consisting of a cobalt complex considerably lowers and even cancels the activity of the catalyst.
• the following tests 20 to 31 are carried out in the same type of apparatus allowing long-term tests and according to the same operating conditions as the tests of Example 1.
• the phosphorus / rhodium ratio is close to 100.
• the cobaltdiene system is added after a certain time of aging of the catalyst (HRhCO (P ⁇ 3 ) 3 ).
• the following tests 32 to 34 relate to the hydroformylation of hexene-1, and were carried out in a 200 ml stainless steel autoclave equipped with an agitator, a temperature measurement and a pipe intended for gas supply. 10 ml of tolene, 10 ml of hexene-1, 40 mg of hydridocarbonyltristriphenylphosphine rhodium (H Rh CO ((P ⁇ ,) 3 ) and 1.2 g of triphenylphosphine (P ⁇ 3 ) are introduced. cobalt and diene in the proportions indicated in table 3. After closing and starting the stirring, the autoclave is heated to reach a temperature of 80 ° C. The relative pressure is 1 bar. 'autoclave the following partial pressures:
• the total relative pressure, which then reaches 7 bars, is maintained at this value by continuously adding a mixture of H 2 / CO gas in a 1/1 ratio. After 25 minutes of reaction, the stirring is cut, the gas supply, the autoclave is cooled and degassed. The reaction mixture is analyzed by gas phase chromatography and the productivity is expressed in grams of aldehydes formed per hour and per gram of. rhodium (g / hxgRh).
• Example 32 is given for comparison.

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• 1983
  • 1983-04-22 FR FR8306649A patent/FR2544713B1/fr not_active Expired
• 1984
  • 1984-04-24 DE DE8484400822T patent/DE3462882D1/de not_active Expired
  • 1984-04-24 JP JP59502047A patent/JPS60501399A/ja active Granted
  • 1984-04-24 EP EP84400822A patent/EP0127501B1/fr not_active Expired
  • 1984-04-24 WO PCT/FR1984/000115 patent/WO1984004299A1/fr not_active Ceased
  • 1984-04-24 US US06/694,556 patent/US4599323A/en not_active Expired - Fee Related
  • 1984-04-24 AT AT84400822T patent/ATE26256T1/de not_active IP Right Cessation

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