Preparation and application of catalyst for synthesizing sustainable aviation fuel from biomass pyrolysis gas

Abstract

The invention discloses preparation and application of a sustainable aviation fuel catalyst synthesized by biomass pyrolysis gas. The catalyst is composed of a composite material of metal cobalt and carbon. The method comprises the following steps: 1) preparation of a metal cobalt and carbon composite catalyst precursor: weighing cobalt salt, dissolving the cobalt salt in acetonitrile and N 'N-dimethylformamide, adding acetonitrile and an N, N-dimethylformamide buffer layer in a certain proportion between the cobalt salt and the N, N-dimethylformamide buffer layer, slowly adding an acetonitrile and N, N-dimethylformamide solution containing terephthalic acid, and carrying out ultrasonic treatment to obtain the metal cobalt and carbon composite catalyst precursor; standing at room temperature until a purple precipitate is separated out, washing with N, N-dimethylformamide and dichloromethane for three times respectively, and performing vacuum drying to obtain a cobalt-based coordination polymer precursor; and 2) placing the coordination polymer precursor in a crucible of a tubular furnace, and reacting for a certain time at a certain temperature in an inert gas atmosphere to obtain the metal cobalt and carbon composite material. And 3) preparing a sustainable aviation fuel catalyst by taking the metal cobalt and carbon composite material as biomass pyrolysis gas, and testing the performance of the sustainable aviation fuel catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of sustainable aviation fuel preparation, and specifically relates to the preparation and application of a catalyst for synthesizing sustainable aviation fuel from biomass pyrolysis gas. Background Art

[0002] At present, the "dual carbon strategy" has become a global consensus. On October 7, 2022, at the International Civil Aviation Organization (ICAO) Assembly, representatives of 193 UN member states unanimously agreed to achieve the goal of net zero emissions in the aviation industry by 2050. According to the Regulation of the European Parliament and the Council on Ensuring a Fair Competition Environment for Sustainable Air Transport promulgated by the European Union in October 2023, in order to combat climate change, airlines will be required to use sustainable aviation fuel (SAF) from 2025. The proportion of SAF use will reach at least 2% in 2025, and will increase every five years thereafter, increasing to 6% by 2030, 20% by 2035, and finally reaching 70% by 2050. As early as December 2021, the Civil Aviation Administration of China pointed out in the "Special Plan for Green Development of Civil Aviation" that it is necessary to promote breakthroughs in the commercial application of sustainable aviation fuel, strive to achieve a sustainable aviation fuel consumption of more than 20,000 tons in 2025, and a cumulative consumption of 50,000 tons during the planning period. Therefore, the application of sustainable aviation fuel is crucial to promoting the green transformation of the civil aviation industry at home and abroad.

[0003] The present invention proposes a method for preparing a metal cobalt and carbon composite catalyst by one-step pyrolysis using a cobalt-based coordination polymer as a precursor, and applies the method to the catalytic reaction of preparing sustainable aviation fuel from biomass pyrolysis gas. The synthesis method of the present invention has the characteristics of simple operation and strong repeatability; the metal cobalt and carbon composite catalyst synthesized by the present invention shows excellent catalytic performance. Summary of the invention

[0004] The purpose of the present invention is to provide a method for synthesizing a metal cobalt and carbon composite catalyst with simple experimental operation and strong repeatability, and to apply the method to the field of preparing sustainable aviation fuel from biomass pyrolysis gas.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] The preparation method and application of a metal cobalt and carbon composite catalyst include the following steps: 1) Preparation of a metal cobalt and carbon composite catalyst precursor: weigh a cobalt salt and dissolve it in acetonitrile and N,N-dimethylformamide, add a certain proportion of acetonitrile and N,N-dimethylformamide buffer layer in the middle, slowly add acetonitrile and N,N-dimethylformamide solution containing terephthalic acid, stand at room temperature until a purple precipitate is precipitated, wash it with N,N-dimethylformamide and dichloromethane three times respectively, and vacuum dry it to obtain a cobalt-based coordination polymer precursor; 2) place the coordination polymer precursor in a crucible of a tubular furnace, react at a certain temperature for a certain time under an inert gas atmosphere to obtain a metal cobalt and carbon composite material. 3) Use the metal cobalt and carbon composite material as a catalyst for synthesizing sustainable aviation fuel from biomass pyrolysis gas and test its performance.

[0007] Preferably, the catalyst is used in the preparation of sustainable aviation fuel by biomass pyrolysis gas, and the conversion rate reaches 68.8% in 70 hours. 5+ The selectivity reached 81.1%.

[0008] Preferably, in step 1), Co 2+ Derived from Co(CH 3 COO 2 ·4H 2 O, the ratio of its mass (mg) to the volume (mL) of N, N-dimethylformamide and the volume (mL) of acetonitrile is 20:1:2, the ratio of the volume (mL) of N, N-dimethylformamide and the volume (mL) of acetonitrile in the buffer layer is 1:1, and the ratio of the mass (mg) of terephthalic acid to the volume (mL) of N, N-dimethylformamide and the volume (mL) of acetonitrile is 20:2:1.

[0009] Preferably, the inert gas in step 2) is Ar gas and N 2 gas.

[0010] Preferably, the certain temperature in step 2) is 600-900°C.

[0011] Preferably, in step 2), the certain period of time is 5 hours.

[0012] Preferably, in step 3), in the application of the metal cobalt and carbon composite material as biomass pyrolysis gas to prepare sustainable aviation fuel, the gas obtained by biomass pyrolysis is purified to mainly contain CO and H 2 , through the gas replenishment process, the ratio is controlled at 1:2. The catalytic reaction is carried out in a fixed bed reactor with a catalyst filling amount of 10 mL, a reaction temperature of 220 ° C, and a reaction pressure of 2 MPa.

[0013] Compared with the prior art, the present invention has the following beneficial effects:

[0014] (1) The present invention prepares a method for synthesizing a metal cobalt and carbon composite catalyst with simple experimental operation and strong repeatability, and applies it to the field of preparing sustainable aviation fuel from biomass pyrolysis gas.

[0015] (2) The catalyst prepared by the present invention is used in the application of biomass pyrolysis gas to prepare sustainable aviation fuel. The conversion rate reaches 68.8% in 70 hours. 5+ The selectivity reached 81.1%. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The X-ray diffraction (XRD) patterns of the metal cobalt and carbon composite material samples synthesized under the conditions shown in Examples 1-4 of the present invention.

[0017] Figure 2 This is a graph showing the conversion rate of the metal cobalt and carbon composite material prepared in Examples 1-4 of the present invention as a catalyst in the application of biomass pyrolysis gas in preparing sustainable aviation fuel.

[0018] Figure 3 The metal cobalt and carbon composite materials prepared in Examples 1-4 of the present invention are used as catalysts in the application of biomass pyrolysis gas to prepare sustainable aviation fuel. 5 + Selective graph. DETAILED DESCRIPTION

[0019] Embodiment 1:

[0020] Weigh 20 mg of Co(CH 3 COO 2 ·4H 2 O was dissolved in a mixture of N, N-dimethylformamide (1 mL) and acetonitrile (2 mL), poured into the bottom of a test tube, and a buffer layer of N, N-dimethylformamide (1 mL) and acetonitrile (1 mL) was slowly dripped, and then 20 mg of terephthalic acid dissolved in N, N-dimethylformamide (2 mL) and acetonitrile (1 mL) were slowly dripped into the test tube, and allowed to stand at room temperature until a purple precipitate was produced. The supernatant was discarded, and the mixture was washed three times with N, N-dimethylformamide and dichloromethane, respectively, and vacuum dried to obtain a cobalt-based coordination polymer precursor. The dried sample was placed in a tubular furnace and heated to 600 °C per minute at 5 °C under an inert atmosphere for 5 hours to obtain a composite material of metal cobalt and carbon. It was used as a catalyst in the preparation of sustainable aviation fuel from biomass pyrolysis gas, and the conversion rate reached 63.4% at 70 hours, and C 5+ The selectivity reached 81.5%.

[0021] Embodiment 2:

[0022] Weigh 40 mg of Co(CH 3 COO 2·4H 2 O was dissolved in a mixture of N,N-dimethylformamide (2mL) and acetonitrile (4mL), poured into the bottom of a test tube, and a buffer layer of N,N-dimethylformamide (2mL) and acetonitrile (2mL) was slowly dripped. Then, N,N-dimethylformamide (4mL) and acetonitrile (2mI) containing 20mg of terephthalic acid were slowly dripped into the test tube and allowed to stand at room temperature until a purple precipitate was produced. The supernatant was discarded, and the mixture was washed three times with N,N-dimethylformamide and dichloromethane, respectively, and vacuum dried to obtain a cobalt-based coordination polymer precursor. The dried sample was placed in a tubular furnace and heated to 700℃ at 5℃ per minute under an inert atmosphere for 5 hours to obtain a composite material of metal cobalt and carbon. It was used as a catalyst in the preparation of sustainable aviation fuel from biomass pyrolysis gas, and the conversion rate reached 41.7% at 70 hours, and C 5+ The selectivity reached 64.1%.

[0023] Embodiment 3:

[0024] Weigh 80 mg of Co(CH 3 COO 2 ·4H 2 O was dissolved in a mixture of N,N-dimethylformamide (4mL) and acetonitrile (8mL), poured into the bottom of a test tube, and a buffer layer of N,N-dimethylformamide (4mL) and acetonitrile (4mL) was slowly dripped. Then, 80mg of terephthalic acid was dissolved in N,N-dimethylformamide (8mL) and acetonitrile (4mL) and slowly dripped into the test tube. It was allowed to stand at room temperature until a purple precipitate was produced. The supernatant was discarded, and the mixture was washed three times with N,N-dimethylformamide and dichloromethane, respectively, and vacuum dried to obtain a cobalt-based coordination polymer precursor. The dried sample was placed in a tubular furnace and heated to 800℃ per minute at 5℃ for 5 hours under an inert atmosphere to obtain a composite material of metal cobalt and carbon. It was used as a catalyst in the preparation of sustainable aviation fuel from biomass pyrolysis gas, and the conversion rate reached 68.8% at 70 hours, and C 5+ The selectivity reached 81.1%.

[0025] Embodiment 4:

[0026] Weigh 20 mg of Co(CH 3 COO 2 ·4H 2O was dissolved in a mixture of N,N-dimethylformamide (1mL) and acetonitrile (2mL), poured into the bottom of a test tube, and a buffer layer of N,N-dimethylformamide (1mL) and acetonitrile (1mL) was slowly dripped. Then, 20mg of terephthalic acid was dissolved in N,N-dimethylformamide (2mL) and acetonitrile (1mL) and slowly dripped into the test tube. It was allowed to stand at room temperature until a purple precipitate was produced. The supernatant was discarded, and the mixture was washed three times with N,N-dimethylformamide and dichloromethane, respectively, and vacuum dried to obtain a cobalt-based coordination polymer precursor. The dried sample was placed in a tubular furnace and heated to 900℃ at 5℃ per minute under an inert atmosphere for 5 hours to obtain a composite material of metal cobalt and carbon. It was used as a catalyst in the preparation of sustainable aviation fuel from biomass pyrolysis gas, and the conversion rate reached 63.5% at 70 hours, and C 5+ The selectivity reached 75.6%.

[0027] The parts of the embodiments herein that are not exhaustive of the midpoint values ​​of the technical scope claimed for protection by the present invention and the new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope claimed for protection by the present invention; at the same time, in all the listed or unlisted embodiments of the scheme of the present invention, each parameter in the same embodiment merely represents an example of its technical solution (i.e., a feasible solution), and there is no strict coordination and limitation relationship between the parameters, wherein the parameters can be replaced with each other without violating the axioms and the claims of the present invention, unless otherwise stated.

[0028] The technical means disclosed in the scheme of the present invention are not limited to the technical means disclosed in the above technical means, but also include technical schemes composed of any combination of the above technical features. The above is a specific implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications are also regarded as the protection scope of the present invention.

[0029] The specific embodiments described herein are merely examples of the spirit of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in similar ways, but they will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. Synthesis and application of a catalyst for preparing sustainable aviation fuel from biomass pyrolysis gas, characterized in that: The following steps are involved: 1) Preparation of metal cobalt and carbon composite catalyst precursor: weigh cobalt salt and dissolve it in acetonitrile and N,N-dimethylformamide, add a certain proportion of acetonitrile and N,N-dimethylformamide buffer layer in the middle, slowly add acetonitrile and N,N-dimethylformamide solution containing terephthalic acid, let it stand at room temperature until purple precipitate is precipitated, wash it with N,N-dimethylformamide and dichloromethane three times respectively, and vacuum dry it to obtain a cobalt-based coordination polymer precursor; 2) Place the coordination polymer precursor in a crucible of a tube furnace, react at a certain temperature for a certain time under an inert gas atmosphere to obtain a metal cobalt and carbon composite material. 3) Use the metal cobalt and carbon composite material as biomass pyrolysis gas to prepare a sustainable aviation fuel catalyst and test its performance.

2. The preparation process of the coordination polymer precursor according to claim 1 2+ It comes from Co(CH3COO)2·4H2O, and the ratio of its mass (mg) to the volume of N,N-dimethylformamide (mL) and the volume of acetonitrile (mL) is 20:1:

2. The ratio of the volume of buffer layer N,N-dimethylformamide (mL) to the volume of acetonitrile is 1:

1. The ratio of the mass (mg) of terephthalic acid to the volume of N,N-dimethylformamide (mL) and the volume of acetonitrile (mL) is 20:2:

1.

3. The method for preparing the metal cobalt and carbon composite material according to claim 1, characterized in that: The calcination treatment is carried out under an inert atmosphere, such as Ar gas or N2 gas.

4. The calcination treatment according to claim 1 is specifically: 600-900°C, calcination for 5 hours.

5. The preparation method according to claims 3 and 4 obtains a composite material of metal cobalt and carbon.

6. The material according to claim 5 is used as a catalyst for preparing sustainable aviation fuel from biomass pyrolysis gas.

7. A method for preparing sustainable aviation fuel using biomass pyrolysis gas as claimed in claim 6, characterized in that the gas obtained by pyrolysis of biomass is purified, mainly CO and H2, and the ratio is controlled at 1:2 through the gas replenishment process. The catalytic reaction is carried out in a fixed bed reactor, the catalyst filling amount is 10 mL, the reaction temperature is 220°C, and the reaction pressure is 2MPa.

8. The sustainable aviation fuel as claimed in claim 7 can be used in the fields of aviation and aerospace.

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