Method for preparing 1, 3-propanediol through hydroformylation of vinyl acetate

Abstract

The invention relates to a method for preparing 1, 3-propanediol through hydroformylation of vinyl acetate. The method mainly solves the problem that the prior art has low 1, 3-propanediol catalyst activity and low selectivity. The method provided through the invention comprises vinyl acetate hydroformylation for 3-acetoxypropanal preparation, 3-acetoxypropanal hydrogenation for 3-acetoxypropanol preparation and 3-acetoxypropanol hydrolysis for 1, 3-propanediol preparation. A hydroformylation catalyst utilizes SiO2, Al2O3 or their mixture as a carrier and active ingredients comprise at least one of platinum metal elements, at least one of alkaline-earth metal elements and at least one of VB and IVA metals. The method well solves the above technical problem and can be used for 1, 3-propanediol industrial production.

Description

technical field

[0001] The invention relates to a method for preparing 1,3-propanediol by hydroformylation of vinyl acetate. Background technique

[0002] 1,3-Propanediol (1.3-PDO) is an important chemical raw material, mainly used in the synthesis of plasticizers, detergents, preservatives, emulsifiers, and also used in food, cosmetics and pharmaceutical industries. Because it is an important polyester fiber monomer, its main use is as a monomer and terephthalic acid to synthesize a new type of polyester material, polytrimethylene terephthalate (PTT).

[0003] The preparation methods of 1,3-propanediol include ethylene oxide one-step method, ethylene oxide two-step method, acrolein hydration method, acetaldehyde-formaldehyde condensation method, acrylate method, biological method, vinyl acetate hydroformylation, etc. At present, the industrialized production method of 1.3-PDO is chemical synthesis, and the international market is mainly monopolized by Degussa Company of Ge...

Examples

Embodiment 1

[0028] The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.40gBa and contain the rhodium acetate two ligands (Rh 2 (OAc) 4 ), Ba(NO 3 ) 2 and ammonium metavanadate (NH 4 VO 3 ) were fully mixed and dissolved in pure water to obtain 400ml of impregnation solution, and the specific surface of 1.0L was 168m 2 / g, spherical SiO with a pore volume of 0.94 and a diameter of 5.6 mm 2 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 100° C. to obtain the catalyst. The Rh content of the catalyst was measured by ICP to be 6.20 g / L, the Ba content to 2.40 g / L, and the V content to 2.90 g / L.

[0029]Synthesis of 1,3-propanediol:

[0030] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydrogen until the pressure is 5.8MPa, increase the stirring speed...

Embodiment 2

[0036] The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.40gBa and contain the rhodium acetate two part of 2.90gSn (Rh 2 (OAc) 4 ), Ba(NO 3 ) 2 and stannous oxalate (SnC 2 o 4 ) is fully mixed and dissolved in an aqueous hydrochloric acid solution with a concentration of 8wt%, to obtain 400ml of soaking solution, and the specific surface of 1.0L is 168m 2 / g, spherical SiO with a pore volume of 0.94 and a diameter of 5.6 mm 2 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 100° C. to obtain the catalyst. The Rh content of the catalyst was determined by ICP to be 6.20 g / L, the Ba content to be 2.40 g / L, and the Sn content to be 2.90 g / L.

[0037] Synthesis of 1,3-propanediol:

[0038] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydr...

Embodiment 3

[0054] The preparation of hydroformylation catalyst: the RhCl containing 5.00gRh, containing 0.50gBe and containing 1.00gV 3 ·6H 2 O, BeCl 2 and VCl 3 Fully mixed and dissolved in 10wt% acetic acid aqueous solution to obtain 400ml of impregnating solution, and the specific surface of 1.0L was 200m 2 / g, spherical Al with a pore volume of 1.00 and a diameter of 5.6mm 2 o 3 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 80° C. to obtain the catalyst. The Rh content of the catalyst measured by ICP was 5.00 g / L, the Be content was 0.50 g / L, and the V content was 1.00 g / L.

[0055] Synthesis of 1,3-propanediol:

[0056] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydrogen until the pressure is 5.8MPa, increase the stirring speed to 800rpm, stir and heat up to the ...

technical field

[0001] The invention relates to a method for preparing 1,3-propanediol by hydroformylation of vinyl acetate. Background technique

[0002] 1,3-Propanediol (1.3-PDO) is an important chemical raw material, mainly used in the synthesis of plasticizers, detergents, preservatives, emulsifiers, and also used in food, cosmetics and pharmaceutical industries. Because it is an important polyester fiber monomer, its main use is as a monomer and terephthalic acid to synthesize a new type of polyester material, polytrimethylene terephthalate (PTT).

[0003] The preparation methods of 1,3-propanediol include ethylene oxide one-step method, ethylene oxide two-step method, acrolein hydration method, acetaldehyde-formaldehyde condensation method, acrylate method, biological method, vinyl acetate hydroformylation, etc. At present, the industrialized production method of 1.3-PDO is chemical synthesis, and the international market is mainly monopolized by Degussa Company of Ge...

Examples

Embodiment 1

[0028] The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.40gBa and contain the rhodium acetate two ligands (Rh 2 (OAc) 4 ), Ba(NO 3 ) 2 and ammonium metavanadate (NH 4 VO 3 ) were fully mixed and dissolved in pure water to obtain 400ml of impregnation solution, and the specific surface of 1.0L was 168m 2 / g, spherical SiO with a pore volume of 0.94 and a diameter of 5.6 mm 2 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 100° C. to obtain the catalyst. The Rh content of the catalyst was measured by ICP to be 6.20 g / L, the Ba content to 2.40 g / L, and the V content to 2.90 g / L.

[0029]Synthesis of 1,3-propanediol:

[0030] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydrogen until the pressure is 5.8MPa, increase the stirring speed...

Embodiment 2

[0036] The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.40gBa and contain the rhodium acetate two part of 2.90gSn (Rh 2 (OAc) 4 ), Ba(NO 3 ) 2 and stannous oxalate (SnC 2 o 4 ) is fully mixed and dissolved in an aqueous hydrochloric acid solution with a concentration of 8wt%, to obtain 400ml of soaking solution, and the specific surface of 1.0L is 168m 2 / g, spherical SiO with a pore volume of 0.94 and a diameter of 5.6 mm 2 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 100° C. to obtain the catalyst. The Rh content of the catalyst was determined by ICP to be 6.20 g / L, the Ba content to be 2.40 g / L, and the Sn content to be 2.90 g / L.

[0037] Synthesis of 1,3-propanediol:

[0038] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydr...

Embodiment 3

[0054] The preparation of hydroformylation catalyst: the RhCl containing 5.00gRh, containing 0.50gBe and containing 1.00gV 3 ·6H 2 O, BeCl 2 and VCl 3 Fully mixed and dissolved in 10wt% acetic acid aqueous solution to obtain 400ml of impregnating solution, and the specific surface of 1.0L was 200m 2 / g, spherical Al with a pore volume of 1.00 and a diameter of 5.6mm 2 o 3 The carrier was immersed in the above impregnating solution, left to stand for 3 hours and dried at 80° C. to obtain the catalyst. The Rh content of the catalyst measured by ICP was 5.00 g / L, the Be content was 0.50 g / L, and the V content was 1.00 g / L.

[0055] Synthesis of 1,3-propanediol:

[0056] Step (1): Add 2.50 mol of toluene, 0.02 mol of hydroformylation main catalyst, 0.20 mol of triphenylphosphine and 1.65 mol of vinyl acetate into a 1L titanium reactor. 2.0MPa, then feed carbon monoxide and hydrogen until the pressure is 5.8MPa, increase the stirring speed to 800rpm, stir and heat up to the ...

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