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Method for preparing acrylic acid through dehydration and oxidization of glycerin in one-step method

A technology of acrylic acid and glycerin aqueous solution, which is applied in the field of catalytic chemistry to achieve the effects of mild reaction conditions, simple separation, and reproducible equipment corrosion.

Inactive Publication Date: 2013-09-18
JIANGSU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Patent US20080183013 uses 90.7% ZrO 2 -9.3% WO 3 , 90%ZrO 2 -10%SO 4 , 91.5%ZrO 2 -8.5%SO 4 Catalyzed one-step dehydration and oxidation of glycerol to prepare acrylic acid. The results show that the conversion rate of glycerol is greater than 97%, but the main product is acrolein, and the highest yield of acrylic acid is only 7.6%.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Take 0.01 mol of ammonium metavanadate and 0.01 mol of ammonium tetramolybdate, mix and dissolve, and maintain a constant temperature of 90 °C until the solid is completely dissolved and condensed by evaporation to form a powder. The evaporated powder was dried in an oven at 150 °C for 4 h, and then calcined at 550 °C for 2 h. The calcined powder was compressed, crushed, and sieved into 20-40 mesh particles. The atomic ratio of molybdenum and vanadium in the prepared molybdenum vanadium composite oxide is 4:1, and the catalyst is named Mo / V=4:1.

[0020] 5 mL of catalyst was loaded into the fixed-bed continuous flow reaction device, and the raw glycerin aqueous solution was continuously sent into the reactor with a non-pulse metering pump. The speed is 0.5 h ?1 , the reaction results are shown in Table 1.

[0021] Table 1

[0022] Reaction time / h Glycerin conversion rate / % Acrylic acid selectivity / % Acrolein selectivity / % 4 97.9 25.4 46.0 8...

Embodiment 2-5

[0024] The catalyst and reaction conditions were the same as in Example 1, only the reaction temperature was changed, and the reaction time was 4 h. The reaction results are shown in Table 2.

[0025] Table 2

[0026] Example Reaction temperature / ℃ Glycerin conversion rate / % Acrylic acid selectivity / % Acrolein selectivity / % 2 200 92.3 20.1 20.2 3 250 96.1 28.9 39.4 4 350 97.5 29.5 35.6 5 400 100 27.7 30.1

Embodiment 6-7

[0028] The catalyst and reaction conditions were the same as in Example 1, only the liquid hourly space velocity was changed, and the reaction time was 4 h. The reaction results are shown in Table 3.

[0029] table 3

[0030] Example Liquid hourly space velocity / h -1 Glycerin conversion rate / % Acrylic acid selectivity / % Acrolein selectivity / % 6 10.8 95.9 21.1 47.2 7 20.0 91.1 18.9 35.6

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PUM

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Abstract

The invention relates to a method for preparing acrylic acid through dehydration and oxidization of glycerin in a one-step method. The method comprises the following steps: by taking a tungsten-vanadium composite oxide or a molybdenum-vanadium composite oxide as a catalyst and taking a glycerin aqueous solution as a raw material, directly dehydrating and oxidizing to prepare acrylic acid and by-product acraldehyde under the conditions of the reaction temperature of 200-400 DEG C and the liquid airspeed of 0.1-100.0h<-1> in the presence of molecular oxygen. The conversion rate of the glycerin can be 100 percent, and the highest yields of the acrylic acid and acraldehyde are respectively 28.9 percent and 43.8 percent. Due to the addition of oxygen, the passivation of the catalyst is inhibited, and the generation of the target product acrylic acid is promoted. The method has the advantages that the acrylic acid with high additional value is prepared by utilizing the biomass glycerin, and the raw material is low in cost and wide in source; the catalyst is adjustable in acidity and oxidability and high in catalytic activity. The process has the characteristics of high reaction speed and high selectivity, the product system is simple in separation, the process flow is safe and environment-friendly, and industrial production can be realized.

Description

technical field [0001] The invention relates to the field of catalytic chemistry, in particular to a method for preparing acrylic acid by catalyzing the dehydration and oxidation of glycerin with a tungsten-vanadium composite oxide and a molybdenum-vanadium composite oxide catalyst. Background technique [0002] Biodiesel is recognized as a new energy source that can replace petrochemical diesel because of its environmental protection and continuous regeneration. Its rapid development leads to a large surplus of by-product glycerol. The development and deep utilization of glycerol, making it a new generation conversion platform from biomass to chemicals has become a recent research hotspot. Synthesis of high value-added derivatives from glycerol with renewability and CO 2 The advantages of zero emission are an effective way to solve the large excess of glycerin. In addition, glycerol is rich in active hydroxyl groups, which can be easily replaced by functional groups to sy...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C57/05C07C51/21C07C47/22C07C45/52B01J23/28B01J23/30
Inventor 殷恒波沈灵沁张长华王爱丽陆秀凤
Owner JIANGSU UNIV