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Supported catalyst for preparing aldehyde by olefin hydroformylation

A supported catalyst, olefin hydroformyl technology, applied in physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, carbon monoxide reaction preparation and other directions, can solve the problem of not mentioned, expensive ligand, catalytic The activity needs to be further improved to achieve the effect of improving the space-time yield, easy operation, and good olefin hydroformylation performance.

Inactive Publication Date: 2006-02-22
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of catalyst does not use molecular sieves as a carrier, its ligands are expensive, and its catalytic activity needs to be further improved.
[0007] Chinese patents ZL93100802.6 and ZL01132718.9 respectively introduce a preparation method of an alkali metal salt-promoted supported water-soluble catalyst and a slurry-type catalyst for hydroformylation of aldehydes, without mentioning the use of ionic liquids and mesoporous molecular sieve carriers

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Under an argon atmosphere, 20 mg of rhodium acetylacetonate dicarbonyl (about 0.0772 mmol) and 243.7 mg of triphenylphosphine trisulfonate (TPPTS) were dissolved in 20 mL of anhydrous methanol, and then 50 mg of dry ionic liquid 1,1 was added , 3,3,-tetramethylguanidine lactate (TMGL), after stirring and mixing evenly, add 1.0 g of mesoporous molecular sieve MCM-41 (particle diameter about 3nm, specific surface area 1041m 2 g -1 ), mixed and stirred for 2 h, and the methanol solvent was removed under vacuum at room temperature to obtain a pale yellow powder-like supported catalyst. In the catalyst system, the phosphine-rhodium molar ratio is about 5 / 1, the rhodium content is 0.8% (wt), and the ionic liquid content is 5% (wt). The above catalyst was transferred to an autoclave, and 8 mL of 1-hexene / toluene containing 25% (wt) of hexene was added, and the 2 Reaction in syngas for 4h at 100°C. The evaluation results are shown in Table 1.

Embodiment 2～5

[0023] As in the catalyst system of Example 1, but the ionic liquid content is 10% (wt) and different phosphine-rhodium ratios are used, and other reaction conditions are the same as in Example 1. The results are shown in Table 2.

[0024]

Embodiment 6

[0026] Catalyst system and reaction condition as embodiment 1, but adopt ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF 6 ), the content is 10% (wt), and other reaction conditions are with embodiment 1. The transformation efficiency 55.1% of 1-hexene, the selectivity of heptanal is 98%, and normal aldehyde is 62.9%, and space-time yield is 3518mmol. h -1 · g-Rh -1 .

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Abstract

Disclosed is a supported catalyst mainly containing sulfonated triphenylphosphine- rhodium complex and is used for preparing aldehyde by hydroformylation of olefin, and relates to an ionic liquid catalyst. It contains solid oxide, sulfonated triphenylphosphine- rhodium complex, sulfonated triphenylphosphine ligand and ionic liquid. The solid oxide is one from hole molecular sieve, SiO2, TiO2, gamma- Al2O3; sulfonated triphenylphosphine- rhodium complex is single-sulfonated triphenylphosphine- rhodium complex, di- sulfonated triphenylphosphine- rhodium complex and tri- sulfonated triphenylphosphine- rhodium complex; and the ionic liquid is 1, 1, 3, 3, - tetramethyl guanidine lactate, 1- butyl- 3- methyl imidazolium tetrafluorborate and 1- butyl- 3- methyl imidazolium hexafluorophosphate. By mass ratio, the solid oxide is among 50%- 90%, the ionic liquid 8%- 49%, and rhodium 0.05%- 2%, and by molecular ratio phosphine to rhodium is 3- 200.

Description

technical field [0001] The invention relates to an ionic liquid catalyst, in particular to a supported ionic liquid complex catalyst for olefin hydroformylation to aldehyde. Background technique [0002] The existing processes for producing aldehydes all use cobalt and rhodium (such as Wilkinson homogeneous phosphine-rhodium catalyst) to catalyze the hydroformylation of olefins. Cobalt catalysts have harsh conditions and require high-pressure reactions; phosphine-rhodium complex catalysts have excellent performance, high aldehyde selectivity, and mild reaction conditions, but it is easy to cause rhodium loss and ligand damage, resulting in short service life of the catalyst. [0003] France Phone-Polenc and Ruhrchemie company (FR, Pat., 2478078) adopt water-soluble sulfonated triphenylphosphine as the rhodium catalyst of ligand for the low-pressure hydroformylation industrial process of propylene to butyraldehyde, and its advantage is that ligand It is very soluble in water...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C45/50
Inventor 袁友珠杨勇邓昌晞戴茂华
Owner XIAMEN UNIV
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