Method for preparing acrolein by dehydrating glycerin

A technology of acrolein and glycerin aqueous solution, which is applied in the preparation of carbon-based compounds, chemical instruments and methods, and the preparation of organic compounds, etc., can solve the problems of glycerin acrolein selectivity to be improved, poor catalyst stability, and complex catalyst preparation, etc., to achieve High conversion rate of glycerin and selectivity of acrolein, low carbon deposition and low cost

Active Publication Date: 2019-06-04
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

[0004] CN104190401A discloses a preparation method of a molybdenum-based composite metal oxide catalyst, the conversion rate of glycerol is greater than 90%, and the selectivity of acrolein can reach more than 40%, but research shows that this type of catalyst has poor stability
CN107115877A discloses a kind of zirconium phosphate as a carrier, impregnated to prepare loaded MO x / ZrP catalyst method, the glycerol conversion rate is 80-100%, but as the reaction time prolongs, the activity decreases
CN106966878A discloses a method for preparing acrolein by catalyzing glycerin dehydration with double-shell ZSM-5 molecular sieves. The catalyst improves the conversion rate of glycerin and the selectivity of acrolein, but the preparation of the catalyst is relatively complicated
At present, the main problem faced by catalysts for dehydration of glycerol to acrolein is that the catalyst is easily deactivated due to carbon deposition, and the conversion rate of glycerin and the selectivity of acrolein need to be improved.

Method used

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  • Method for preparing acrolein by dehydrating glycerin

Examples

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Comparison scheme
Effect test

Embodiment 1

[0025] Take 30g of HZSM-5 molecular sieve (Si / Al=25.8), add it to 310ml of 0.12mol / L oxalic acid solution, stir magnetically at 78°C for 1.1h, then filter and wash until neutral, and dry in an oven at 120°C for 12h; Take 10 g of the obtained molecular sieve and add it to 210 ml of 0.22 mol / L NaOH solution, stir magnetically at 88°C for 1.2h, then filter and wash until neutral, and dry in an oven at 120°C for 12h. Add the obtained molecular sieve into 0.90mol / L ammonium nitrate solution, the solid-to-liquid ratio is 1:30, stir magnetically at 85°C for 2h, then filter and wash, dry in an oven at 120°C for 12h, and then place in a muffle furnace for 410 Baking at ℃ for 3.1h.

[0026] The above-mentioned catalyst (0.5 g, 20-40 mesh) was loaded into a fixed-bed reactor, and activated at 500° C. for 2 h under a nitrogen atmosphere (20 ml / min). Carry out the continuous reaction of glycerol dehydration system acrylic acid subsequently, be that 16wt% glycerol aqueous solution is raw m...

Embodiment 2

[0028] Take 20g of HZSM-5 molecular sieve (Si / Al=31.2), add it to 260ml of 0.11mol / L oxalic acid solution, stir magnetically at 75°C for 1.2h, then filter and wash until neutral, and dry in an oven at 120°C for 12h; Take 10 g of the obtained molecular sieve and add it to 310 ml of 0.21 mol / L NaOH solution, stir magnetically at 83°C for 0.8h, then filter and wash until neutral, and dry in an oven at 120°C for 12h. Add the obtained molecular sieve into 0.90mol / L ammonium nitrate solution, the solid-to-liquid ratio is 1:30, stir magnetically at 85°C for 2h, then filter and wash, dry in an oven at 120°C for 12h, and then place it in a muffle furnace for 450 Baking at ℃ for 3.5h.

[0029] The above-mentioned catalyst (0.5 g, 20-40 mesh) was loaded into a fixed-bed reactor, and activated at 500° C. for 2 h under a nitrogen atmosphere (20 ml / min). Carry out the continuous reaction of glycerin dehydration system acrylic acid subsequently, be that 42wt% aqueous glycerin is raw materia...

Embodiment 3

[0031] Take 35g of HZSM-5 molecular sieve (Si / Al=37.7), add it to 680ml of 0.10mol / L oxalic acid solution, stir magnetically at 71°C for 1.4h, then filter and wash until neutral, dry in an oven at 120°C for 12h; Add 15 g of the obtained molecular sieves to 580 ml of 0.19 mol / L NaOH solution, stir magnetically at 69°C for 0.7h, then filter and wash until neutral, and dry in an oven at 120°C for 12h. Add the obtained molecular sieve into 0.90mol / L ammonium nitrate solution, the solid-to-liquid ratio is 1:30, stir magnetically at 85°C for 2h, then filter and wash, dry in an oven at 120°C for 12h, and then place in a muffle furnace for 480 Roasting at ℃ for 4.6h.

[0032]The above-mentioned catalyst (0.5 g, 20-40 mesh) was loaded into a fixed-bed reactor, and activated at 500° C. for 2 h under a nitrogen atmosphere (20 ml / min). Carry out the continuous reaction of glycerol dehydration system acrylic acid subsequently, be that 50wt% glycerol aqueous solution is raw material with m...

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Abstract

The invention discloses a method for preparing an acrolein catalyst by dehydrating glycerin. The method comprises the following steps: carrying out acid treatment on a molecular sieve, carrying out alkali treatment, filtering and washing the treated molecular sieve to neutrality, drying the molecular sieve, and carrying out ion exchange and calcining to convert the molecular sieve into a hydrogentype hierarchical porous molecular sieve; and dehydrating glycerin in a fixed bed reaction at a reaction temperature of 280-340 DEG C with the prepared hierarchical porous molecular sieve as the catalyst, a 10-50 wt% aqueous glycerin solution as a raw material and nitrogen as a carrier gas to produce the acrolein. The method has the advantages of simplicity in catalyst preparation and operation,low cost, and the obtained modified molecular sieve material has a high activity, and allows the glycerin conversion rate to be 90-100% and the acrolein selectivity to be 70-85% when applied to the dehydration of glycerin to produce acrolein.

Description

technical field [0001] The invention relates to a method for preparing acrolein by dehydrating glycerin, and belongs to the fields of molecular sieve modification, adsorption material preparation and catalyst preparation. Background technique [0002] With the overcapacity and price drop of glycerol, how to efficiently utilize excess glycerol and convert it into high value-added chemical products has become a research hotspot. Among them, the dehydration of glycerol to acrolein is a promising value-added route for glycerin. As the simplest unsaturated aldehyde, acrolein is an important organic chemical intermediate with active chemical properties. An important use of acrolein is the oxidation to produce acrylic acid, and then further esterification and polymerization of acrylic acid to produce acrylate, which is widely used in textiles, adhesives, coatings and other fields. In addition, acrolein can be used to synthesize 3-methylthiopropanal for the production of methionin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/22C07C45/52B01J29/40B01J37/30B01J37/08
Inventor 徐龙伢杨识途张爽陈福存刘珍妮
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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