Method for preparing aldehyde by hydroformylation of light olefins

Abstract

The invention discloses a method for preparing aldehyde by hydroformylation of low-carbon olefin, which is characterized in that 0.1-2 parts of rhodium composition, 0.3-10 parts of bidentate phosphine ligand, 0.001-0.1 parts of surface active agent and 100-500 parts of de-ionized water are added into a high-pressure autoclave provided with a stirrer and a thermograph according to the part by weight, and are caused to be completely dissolved; synthesis gas containing hydrogen and carbon monoxide with the volume ratio of 1:1 is used for displacing for 3-5 times in the high-pressure autoclave, the pressure of 0.8-1.9MPa needed by the hydroformylation of low-carbon olefin is applied by pressurizing, and then the pressure of the synthesis gas is increased to 2-6MPa; the reaction lasts for 1-4h at the temperature of 6-150 DEG C; the reactant is taken out after being cooled; an aqueous solution layer of the catalyst is separated out, and the product of aldehyde is obtained.

Description

Technical field: [0001] The invention relates to a method for preparing aldehydes by hydroformylation of olefins, and belongs to the field of synthesis of basic organic chemicals. technical background: [0002] The preparation of aldehyde by olefin hydroformylation is one of the important reactions in the field of petrochemical industry, and the propionaldehyde obtained by ethylene hydroformylation is the raw material of medicine, solvent and fungicide. Butyraldehyde is produced by hydroformylation of propylene, and isooctyl alcohol obtained by condensation and hydrogenation of butyraldehyde is the raw material for the production of plasticizer di-isooctyl phthalate, and valeraldehyde, the product of butene hydroformylation, is not only a raw material for the production of fragrances , and its condensation and hydrogenation products are the raw materials for the production of a new generation of safer diisodecyl phthalate, and the world's annual output of aldehydes produced ...

AI Technical Summary

Problems solved by technology

Angew.Chem.Int.Ed.Engl.1993, 32, 1524-1544, published HRh(CO)(TPPTS) 3 (Three-trisulfonated triphenylphosphine-hydrocarbonyl rhodium) and TPPTS (m-trisulfonated triphenylphosphine trisodium salt) are used for the hydroformylation of propylene, but the positive and isotropic ratio of the product not satisfactory

"Petrochemical Industry" 2000, 29 (9), 654-658 published a water-soluble phosphine ligand TPPTS and a rhodium complex catalyst HRh (CO) (TPPTS) 3 The hydroformylation reaction of butene in the water / organic two-phase system with the composite catalyst system composed of CTAB (cetyltrimethylammonium bromide) and disodium hydrogen phosphate, CTAB-Na 2 HPO 4 Although the introduction of increased the activity of the hydroformylation reaction, the selectivity of forming normal aldehydes was not high, and the basic Na 2 HPO 4 Introduced into the system, it is easy to cause the condensation of aldehydes

"Fine Petrochemical Progress" 2003, 4 (2) 5-7 and 2004, 5 (6), 35-38 published the composition of water-soluble rhodium phosphine complexes and cationic surfactant cetyltrimethylammonium bromide In the hydroformylation reaction of butene in a water-organic two-phase medium, the positive-to-isotropic ratio of the resulting product is not high, and the amount of surfactant is high, which easily causes emulsification of the solution and makes it difficult to separate the two phases.

Chinese patent CN1562932 discloses a method for preparing valeraldehyde by hydroformylation of butene in an ionic liquid of methyl butyl imidazolium tetrafluoroborate, although the method is easy to realize the separation of catalyst and product, but the ionic liquid Difficult to prepare, high cost, difficult to achieve industrialization

Chinese patent CN200410081352.0 discloses a Rh-TPP (triphenylphosphine)-phosphotungstic heteropolyacid supported on SiO 2 The heterogeneous catalyst above realizes the hydroformylation of butene to prepare valeraldehyde, but this method uses SiO 2 Supporting hydrocarbon-soluble triphenylphosphine-rhodium complexes, the oxidation of triphenylphosphine by trace oxygen in the reaction system and the leaching of olefins and aldehydes can easily lead to the loss of the catalyst

German patent DE-A4040315 discloses a hydroformylation reaction of sulfonated water-soluble bidentate phosphine ligands BISBIS and BINAS to olefins, and Appl.Catal.A, 2003, 251 (1), 181-185, published RhCl(CO)(TPPTS) 2 The catalyst system composed of bidentate phosphine ligand BISBIS is used for the hydroformylation reaction of butene. However, the catalytic system composed of these bidentate phosphine has a lower reaction rate for the hydroformylation of light olefins in the absence of surfactants. Low, requires higher reaction temperature

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