CN-122010706-A - Condensation reaction method of mixed bio-oleyl aldehyde ketone compound and aviation fuel precursor

Abstract

The invention belongs to the technical field of biomass energy conversion, and particularly discloses a condensation reaction method of a mixed bio-oleyl aldehyde ketone compound and an aviation fuel precursor. The condensation reaction method comprises 1) a first condensation stage, wherein mixed reactants comprising cyclopentanone, valeraldehyde, furfural and 2-pentanone are subjected to condensation reaction at 30-90 ℃ in the presence of an acid-base bifunctional catalyst, 2) a separation step, wherein the mixture obtained after the reaction in the step 1) is separated to obtain a fraction rich in a first condensation product and a fraction rich in unreacted reactants, and 3) a second condensation stage, wherein the fraction rich in unreacted reactants obtained in the step 2) is subjected to condensation reaction at 90-130 ℃ in the presence of the acid-base bifunctional catalyst to obtain a second condensation product. According to the invention, the complex reaction network is selectively regulated and controlled through coupling step reaction and physical separation, so that the directional synthesis of aviation fuel precursors is realized.

Inventors

• HE JING
• ZHU YANRU
• REN WENQIAN
• AN ZHE
• ZHANG JIAN
• SHU XIN

Assignees

• 北京化工大学
• 衢州资源化工创新研究院

Dates

Publication Date

20260512

Application Date

20251224

Claims (9)

1. 1. A method for the condensation reaction of a mixed biooleyl aldehyde ketone compound, comprising: 1) A first condensation stage, in which a mixed reactant containing cyclopentanone, valeraldehyde, furfural and 2-pentanone is subjected to condensation reaction at 30-90 ℃ in the presence of an acid-base bifunctional catalyst; 2) A separation step of separating the mixture obtained after the reaction in the step 1) to obtain a fraction rich in the first condensation product and a fraction rich in unreacted reactants; 3) And a second condensation stage, namely carrying out condensation reaction on the fraction rich in unreacted reactants obtained in the step 2) at the temperature of 90-130 ℃ in the presence of an acid-base bifunctional catalyst to obtain a second condensation product.
2. 2. The condensation reaction method of a mixed bio-oleyl aldehyde ketone compound according to claim 1, wherein the acid-base bifunctional catalyst is selected from magnesium-aluminum layered double metal oxide, magnesium-aluminum-zirconium layered double metal oxide, magnesium-zirconium composite metal oxide.
3. 3. The condensation reaction method of a mixed bio-oleyl aldehyde ketone compound according to claim 2, wherein the acid-base bifunctional catalyst is a magnesium aluminum zirconium layered bimetallic oxide.
4. 4. The condensation reaction method of a mixed biooleyl aldehyde ketone compound according to claim 1, wherein in step 1), the reaction temperature is 50-90 ℃ and the reaction time is 1-24 hours.
5. 5. The condensation reaction method of a mixed biooleyl aldehyde ketone compound according to claim 1, wherein in the step 2), the separation method is atmospheric distillation, vacuum distillation or rectification.
6. 6. The method of condensation reaction of a mixed biooleyl aldehyde ketone compound according to claim 1, wherein the first condensation product comprises one or more of cyclopentanone-valeraldehyde, cyclopentanone-furfural, valeraldehyde-furfural cross condensation products.
7. 7. The condensation reaction method of a mixed biooleyl aldehyde ketone compound according to claim 1, wherein in the step 3), the reaction temperature is 100-130 ℃ and the reaction time is 2-24 hours.
8. 8. The method for the condensation reaction of a mixed biooleyl aldehyde ketone compound according to claim 1, wherein the second condensation product comprises a self-condensation of 2-pentanone or a cross-condensation product with residual cyclopentanone.
9. 9. An aviation fuel precursor produced by the condensation reaction method of the mixed bio-oleyl aldehyde ketone compound according to any one of claims 1 to 8.

Description

Condensation reaction method of mixed bio-oleyl aldehyde ketone compound and aviation fuel precursor Technical Field The invention belongs to the technical field of biomass energy conversion, and particularly relates to a condensation reaction method of a mixed bio-oleyl aldehyde ketone compound and an aviation fuel precursor. Background The bio-oil is a main product obtained by rapid pyrolysis and liquefaction of biomass, has complex components and is rich in various oxygen-containing compounds such as aldehydes, ketones, phenols and the like. Wherein, aldehydes and ketones compounds, such as cyclopentanone, valeraldehyde, furfural, 2-pentanone, etc., can form oxygenated intermediates with longer carbon chains through aldol condensation reaction. After the intermediate is further subjected to hydrodeoxygenation treatment, the product hydrocarbons meet the specification requirements of aviation fuels on carbon number distribution (mainly C8-C16) and key physical properties (such as freezing point, flash point and heat value), and are regarded as aviation fuel precursors with high added value. The efficient and selective preparation of the precursor is a core step for directionally converting biological oil into green aviation fuel. However, in practical bio-oil refining processes, the aldehyde ketone components are often present in a mixture, which presents a great challenge to directional condensation, and the intrinsic activity of the reactants varies greatly, resulting in runaway reaction selectivity. In the mixed system, the reactivity of different aldehyde ketone components is obviously different. For example, furfural is far more reactive as an electrophile (carbonyl) than ketone components such as cyclopentanone and 2-pentanone due to its strong electron withdrawing effect of the furan ring. Valeraldehyde is also more active than ketones as a linear aldehyde. When they coexist, highly active furfural and valeraldehyde react with each other or self-polymerize preferentially and rapidly, so that not only are these key components consumed in large amounts, but also complex and difficult-to-control byproducts are generated, and chain ketones such as 2-pentanone with lower activity may remain in large amounts due to 'competition failure', resulting in insufficient raw material utilization and low target product selectivity. At present, research on mixed aldehyde ketone condensation is focused on developing a novel efficient catalyst, and although the overall conversion rate can be improved to a certain extent, the bottleneck problem caused by the activity difference is difficult to solve fundamentally. For example, the use of catalysts with strongly basic sites may exacerbate the reaction of all components, resulting in further complexity of the product, while the use of shape selective catalysts may screen portions of the macromolecules, but fail to achieve precise guidance of a particular reaction path. Therefore, there is an urgent need in the art for an innovative process capable of achieving efficient condensation of mixed aldehyde ketone components in biological oils in order to achieve refined control of product distribution and effective simplification of separation processes while improving the overall conversion of raw materials. Disclosure of Invention In view of the above, the present invention aims to provide a condensation reaction method of a mixed bio-oil aldehyde ketone compound and an aviation fuel precursor, which solve the technical problems of poor reaction selectivity, insufficient raw material utilization, etc. caused by the difference of reactivity and boiling point interweaving in a bio-oil mixed aldehyde ketone system by fractional condensation. The first aspect of the present invention provides a condensation reaction method of a mixed bio-oleyl aldehyde ketone compound, the condensation reaction method comprising: 1) A first condensation stage, in which a mixed reactant containing cyclopentanone, valeraldehyde, furfural and 2-pentanone is subjected to condensation reaction at 30-90 ℃ in the presence of an acid-base bifunctional catalyst; 2) A separation step of separating the mixture obtained after the reaction in the step 1) to obtain a fraction rich in the first condensation product and a fraction rich in unreacted reactants; 3) And a second condensation stage, namely carrying out condensation reaction on the fraction rich in unreacted reactants obtained in the step 2) at the temperature of 90-130 ℃ in the presence of an acid-base bifunctional catalyst to obtain a second condensation product. The second aspect of the invention provides an aviation fuel precursor prepared by the condensation reaction method of the mixed bio-oil aldehyde ketone compound. Compared with the prior art, the invention has the following beneficial effects: 1. The condensation reaction method of the invention selectively regulates and controls the complex reaction network through coupling fractional r