Method for preparing aldehyde through linear chain olefin hydroformylation

Abstract

The invention relates to a method for preparing aldehyde through linear chain olefin hydroformylation. According to the method, a continuous reaction mode is used for performing olefin hydroformylation reaction in a homogeneous catalyst system; a catalyst is a composite catalysis system composed of a rhodium complex, a biphenyl backbone or biphenyl backbone diphosphine ligands and triphenylphosphine or triphenyl phosphate monophosphorous ligands; a reaction solvent comprises butyraldehyde, valeraldehyde, toluene or isodecanol; when the catalyst system uses propylene or butene-1 as raw materials under the condition of a low molar ratio of the diphosphine ligands to the rhodium complex, contents of the aldehyde generated by hydroformylation of the propylene and the butene-1 is larger than 97% and 95% respectively; and when the catalyst system uses a mixture of the butene-1 and butene-2 as raw materials, and the content of n-valeraldehyde in hydroformylation reaction products can reach above 85%.

Description

technical field [0001] The invention relates to a method for preparing aldehyde by homogeneously catalyzing olefin hydroformylation. Background technique [0002] The hydroformylation of propylene or butene to produce aldehyde, and then the bimolecular aldehyde is condensed and hydrogenated to produce 2-ethylhexanol or 2-propylheptanol, which is a method for preparing alcohol for plasticization; butyraldehyde and pentylene Aldehydes and their hydrogenation products butanol and pentanol are important raw materials for organic synthesis. [0003] Hydroformylation of olefins to produce aldehydes was the earliest developed cobalt carbonyl catalyst system, because it catalyzes the hydroformylation of olefins under high temperature and pressure, the conditions are harsh, and the proportion of normal aldehydes is low, and there are many by-products. Therefore, it was later replaced by a rhodium-phosphine catalyst system with much higher catalytic activity and better aldehyde selec...

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Problems solved by technology

[0005] Triphenylphosphine is cheap, and the catalyst system composed of it and a rhodium complex has good catalytic activity and stability, and has been widely used for catalyzing propylene hydroformylation to produce butyraldehyde (Forhning, C.D.; Kohlpaintner, C.W.; in Applied Homogeneous Catalysis With Organometallic compounds, Ed. By Cornils, B.; Herrmann, W. A.: VCH, Weinheim, New York, 1996, Vol. 1, p29-104: Bhaduri, S., Mukesh, D. Homogeneous Catalysis: Mechanisms and Industrial Applications, John Wiley &sons, 2000, p85-103), but the ratio of generating n-butyraldehyde is about 87--90%, which cannot meet the requirements of products that need to produce higher n-aldehyde content; The catalytic activity of formylation is very low, so it can only be used for the hydroformylation of butene-1 to valeraldehyde, or the hydroformylation of raw materials with more than 50% butene-1 content in mixed butenes to valeraldehyde (ZL200610042655. 0), but the content of normal aldehydes is low; U.S. patents (US5463147, US5410072) report two-stage butene hydroformylation to valeraldehyde, the first stage uses a water-soluble rhodium catalyst, and the second stage uses cobalt carbonyl Catalyst, the catalytic reaction pressure is high, and the process is complicated

Foreign reports on the hydroformylation of α-olefins and internal olefins catalyzed by catalyst systems composed of diphosphine or binaphthyl-structured bisphosphine and rhodium complexes, including the catalytic hydrogenation of butene-2 Acylation reaction;【van Leeuwen, P.W.N.M. Angew. Chem. 1999, 111, 349; Angew. Chem. Int. Ed.,1999, 38, 336; Organometallics, 1999, 18, 4765; Selent D., Boener A., 2001, 113, 1739; Angew. Chem. Int. Ed., 2001, 40, 1696; Klein H., Blller M., Angew. Chem. 2001, 113, 3505; . 2001, 40, 3408.] They show good catalytic activity and selectivity to form n-valeraldehyde, but because the phosphine ligand is expensive, there is no industrial application; Catalyst system composed of phosphite, bisphosphoramidite and rhodium complex catalyzes the hydroformylation of propylene, butene and long-chain olefins and its application [(UCC) EP213639, 1987; US 4748261, 1988; ( DSM / DU Pont) WO97133854, 1997; CN 101332437A; CN1857776A; CN 1029774C; CN 101768060A; van der Slot,S.C. van Leeuwen, P.W.N.M. Organometallics, 2002,21,3873; Magee, M. P., Luo, W., Hersh, W. H. Organometallics, 2002, 21, 362; Zhang, X., J.Am. Chem. Soc., 2006, 128, 16058. ]; The catalyst system composed of bisphosphite or bisphosphoramidite ligand and rhodium complex has high catalytic Activity and high selectivity to generate n-valeraldehyde, catalyzing 2-butene hydroformylation reaction also has good activity, but the stability of bisphosphite ligands is poor, and the alkyl hydroxyphosphonic acid generated by its degradation will form a gel , resulting in pipeline blockage (Contemporary Petroleum and Petrochemical, 2002 (10), 15), when bisphosphoramidite ligands encounter trace amounts of water or oxygen, they will easily lead to hydrolysis and oxidation, resulting in a decrease in catalyst activity, especially the selectivity to form normal aldehydes It is greatly reduced and cannot meet the stability requirements of industrial production, so it is necessary to explore new catalyst system

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