A Pt / In2O3 supported catalyst derived from an indium metal organic framework and its preparation method and application

Abstract

The present invention relates to the field of catalytic thermal cracking of oils and fats, and in particular to a Pt / In2O3 supported catalyst derived from an indium metal organic framework and a preparation method and application thereof. The preparation method comprises the following steps: (1) 3+ The soluble salt, terephthalic acid, surfactant and solvent are stirred and mixed to obtain a mixed solution; (2) the mixed solution is placed in a reactor and reacted at 80-110°C for 15-25h; (3) the product obtained in step (2) is centrifuged, washed and dried to obtain a MIL-68 (In) metal organic framework, which is then calcined to obtain an In2O3 carrier; (4) the In2O3 carrier obtained in step (3) is dispersed in a Pt metal precursor solution, and a reducing agent is added for reduction to obtain a Pt / In2O3 supported catalyst. The Pt / In2O3 supported catalyst prepared by the present invention exhibits good deoxygenation activity and high aromatic selectivity in stearic acid catalytic thermal cracking reaction due to the synergistic effect of the metal and the carrier.

Description

Technical Field

[0001] The present invention relates to the field of catalytic thermal cracking of oils and fats, and in particular to a Pt / In2O3 supported catalyst derived from an indium metal organic framework and a preparation method and application thereof. Background Art

[0002] Due to the rapid development of modern society and the continuous increase in the global population, the demand for fossil energy has increased year by year, which has also led to a large amount of greenhouse gas emissions, causing severe environmental problems such as global warming. The new biomass energy, as the second most consumed energy after coal, oil and natural gas, can be converted into solid, liquid and gaseous fuels. It is a renewable energy source and the only renewable carbon source. It is estimated that by the middle of the 21st century, biomass alternative fuels will account for 40% of the world's total consumption, so the development of biomass energy will be of great significance.

[0003] Oil is an important biomass resource, and its resource utilization has application prospects. The resource utilization of oil is mainly catalytic thermal cracking of oil. The deoxygenation efficiency and selectivity of oil are the key to product quality. In order to facilitate the study of reaction characteristics, fatty acids are often used as model compounds of oil. According to the degree of saturation, they can be divided into saturated fatty acids and unsaturated fatty acids. Common fatty acids in oil include lauric acid (C 12:0 ), myristic acid (C 14:0 ), palmitic acid (C 16:0 ), stearic acid (C 18:0 ) and palmitic acid (C 16:1 ), oleic acid (C 18:1 ), linoleic acid (C 18:2 ), linolenic acid (C 18:3 ) and other unsaturated acids. After deoxygenation treatment, fatty acids can effectively reduce the acid value and improve combustion characteristics. Usually, the corresponding main deoxygenation products are long-chain alkanes, long-chain olefins and aromatic products. All three products are the main components of high-quality biodiesel, kerosene and aviation kerosene. In order to achieve the goal of carbon neutrality, the catalytic deoxygenation of oils and fats to prepare biofuels has important research significance and development prospects.

[0004] At present, a large number of preparation studies on fatty acid deoxygenation catalysts are concentrated in batch reactors, which are only suitable for laboratory research, prone to low production capacity, and each operation requires re-feeding, complex engineering, and the main products generated are mainly long-chain alkanes, while the selectivity for olefins and aromatic products with higher value is low. At the same time, most catalysts have poor reusability and stability. Therefore, it is very important to develop a metal catalyst with good deoxygenation activity and high aromatic selectivity. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art and to provide a Pt / In2O3 supported catalyst derived from an indium metal organic framework and a preparation method and application thereof.

[0006] In order to solve the above technical problems, the technical solutions provided by the present invention are as follows:

[0007] The invention discloses an indium metal organic framework-derived Pt / In2O3 supported catalyst, which is composed of a Pt NPs active component and an In2O3 carrier.

[0008] In a more preferred embodiment, the Pt content is 2wt%-3wt%. By selecting an appropriate Pt content range, the best catalytic effect can be obtained within the most suitable preparation cost range.

[0009] In a more preferred embodiment, the particle size of the Pt is 1-3 nm, which is a preferred Pt particle size range of the present invention, and it allows the Pt to be evenly distributed on the In2O3 carrier.

[0010] In a more preferred embodiment, the particle size of the Pt / In2O3 is 200-500nm.

[0011] In a more preferred embodiment, the molar ratio of the indium salt to terephthalic acid is in the range of 1:1-3.

[0012] The present invention provides a method for preparing a Pt / In2O3 supported catalyst derived from an indium metal organic framework, comprising the following steps:

[0013] (1)In 3+ The soluble salt, terephthalic acid, surfactant and solvent are stirred and mixed uniformly to obtain a mixed solution;

[0014] (2) placing the mixed solution in a reaction kettle and reacting at 80-110° C. for 15-25 hours;

[0015] (3) The product obtained in step (2) is centrifuged, washed and dried to obtain a MIL-68 (In) metal organic framework, which is then calcined to obtain an In2O3 carrier;

[0016] (4) Dispersing the In2O3 carrier obtained in step (3) in one of the solutions containing HPtCl6, (NH4)2PtCl4 and K2PtCl4, and then adding a reducing agent for reduction to obtain a Pt / In2O3 supported catalyst.

[0017] It should be noted that terephthalic acid is used as an organic ligand in the present invention. 3+ Soluble salts form In-MOF, while surfactants act as regulators to regulate the morphology of In-MOF.

[0018] In a more preferred embodiment, In 3+ The molar ratio of the soluble salt to terephthalic acid is 1:1-3. Under this ratio, In 3+ The soluble salts can be successfully synthesized with terephthalic acid into In-MOF.

[0019] In a more preferred embodiment, the surfactant and In 3+ The molar ratio of soluble salts is 0-1:1.

[0020] In a more preferred embodiment, the In 3+ The soluble salt is a combination of one or more of indium nitrate, indium iodide and indium chloride; preferably, the In 3+ The soluble salt is indium nitrate. It is worth noting that indium nitrate is the most preferred because in the process of synthesizing In-MOF, compared with indium chloride and indium iodide, chlorine and iodine will exist in In-MOF, and after calcination, the catalytic performance of Pt / In2O3 will deteriorate.

[0021] In a more preferred embodiment, the surfactant is a combination of one or more of polyvinyl pyrrolidone, triethanolamine, and hexadecyltrimethylammonium chloride.

[0022] In a more preferred embodiment, the reducing agent is a combination of one or more of sodium borohydride, lithium aluminum hydride, and potassium borohydride.

[0023] In a more preferred embodiment, in step (3), the calcination conditions are: calcination at 400-600° C. for 2-10 h in air atmosphere.

[0024] In a more preferred embodiment, in step (4), the In2O3 carrier is first dissolved in an organic solvent and ultrasonicated, and then the Pt metal precursor solution is added and stirred, and the stirring time is 1-3 hours.

[0025] In a more preferred embodiment, in step (4), the reduction reaction time is 1-3 hours.

[0026] The present invention provides the use of the Pt / In2O3 supported catalyst prepared by the preparation method described above in the non-hydrogenation catalytic deoxygenation of fatty acids.

[0027] In summary, the present application includes at least one of the following beneficial technical effects:

[0028] (1) The present invention adopts the MOF derivatization method to prepare the indium metal organic framework-derived Pt / In2O3 supported catalyst, which has a simple preparation process and is convenient for mass production.

[0029] (2) The Pt / In2O3 supported catalyst prepared by the present invention exhibits good deoxygenation activity and aromatics selectivity in stearic acid catalytic thermal cracking.

[0030] Other features and beneficial effects of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other beneficial effects of the present invention can be realized and obtained by the structures particularly pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. The positional relationships described in the drawings in the following description are based on the directions in which the components are drawn in the diagrams, unless otherwise specified.

[0032] Figure 1 This is the SEM image of In2O3 in Example 1 provided by the present invention.

[0033] Figure 2 This is the XRD diagram of In2O3 in Example 1 provided by the present invention.

[0034] Figure 3 This is the TEM image of Pt / In2O3 in Example 1 provided by the present invention.

[0035] Figure 4 This is a performance diagram of In2O3 and Pt / In2O3 of the present invention.

[0036] Figure 5 Graph showing the performance of different Pt / In2O3 substrates of the present invention. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments; the technical features designed in different implementation modes of the present invention described below can be combined with each other as long as they do not conflict with each other; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0038] In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meanings as those generally understood by ordinary technicians in the field to which the present invention belongs, and cannot be understood as limiting the present invention; it should be further understood that the terms used in the present invention should be understood to have the same meanings as these terms in the context of this specification and in the relevant fields, and should not be understood in an idealized or overly formal sense, unless explicitly defined in the present invention.

[0039] The technical solution of the present invention is further illustrated and described below through specific embodiments, but the protection scope of the present invention is not limited thereto.

[0040] Example 1

[0041] 2g of indium nitrate and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mL of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100°C for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60°C overnight to obtain the MIL-68 (In) metal organic framework and heated to 500°C at a rate of 10°C / min, and calcined at a constant temperature for 2h to obtain the metal organic framework-derived In2O3 carrier. Figure 1 , 2 is the SEM and XRD images of the In2O3 carrier after calcination, proving the successful synthesis of In2O3 and the particle size range of 200-500nm.

[0042] 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. Subsequently, 1.93 mmol of HPtCl6·6H2O was added and stirring continued for 1 h. After stirring, 10 mL of NaBH4 (0.1 M) aqueous solution was added and stirred vigorously for 1 h. Finally, the product was collected by centrifugation, washed three times with ethanol, and dried to obtain a Pt / In2O3 supported catalyst (catalyst number A). Figure 3 Transmission electron microscopy image of successfully loaded Pt particles.

[0043] 20 mg of catalyst was loaded into a 10 mL quartz tube of the secondary reactor of the thermal cracking-gas chromatography / mass spectrometry device, and 0.5 mg of solid stearic acid was injected through the feeder. After being gasified in the primary reactor, it was flowed to the catalyst along with the carrier gas to react. After the reaction was completed, GC-MS was used for detection and analysis. The product conversion rate was 100%, the deoxygenation rate was 97%, and the aromatic selectivity was 84%.

[0044] Example 2

[0045] Dissolve 2g of indium iodide, 2g of indium nitrate and 1g of terephthalic acid (H2BDC) in 5mL of N,N-dimethylformamide (DMF), add 0.1mL of triethanolamine (TEOA) and stir for 15min. Finally, transfer the obtained mixed solution to a 100mL autoclave with a polytetrafluoroethylene liner and react at 100℃ for 24h. After the reaction, centrifuge the obtained solution to obtain a white precipitate, wash it twice with ethanol, dry it at 60℃ overnight to obtain the MIL-68(In) metal organic framework and heat it to 500℃ at a rate of 10℃ / min, calcine it at a constant temperature for 2h, and obtain the metal organic framework derived In2O3 carrier. Dissolve 200mg of the calcined In2O3 in 40mL of methanol and ultrasonicate it for 30min. Subsequently, 1.93 mmol of HPtCl6·6H2O was added and stirring continued for 1 h. After stirring, 10 mL of NaBH4 (0.1 M) aqueous solution was added and stirred vigorously for 1 h. Finally, the product was collected by centrifugation, washed three times with ethanol, and dried to obtain a Pt / In2O3 supported catalyst (catalyst number B).

[0046] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 82%, and the aromatic selectivity was 67%.

[0047] Example 3

[0048] 2g of indium chloride and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mL of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100℃ for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60℃ overnight to obtain the MIL-68(In) metal organic framework and heated to 500℃ at a rate of 10℃ / min, calcined at constant temperature for 2h to obtain the metal organic framework-derived In2O3 carrier. 200mg of calcined In2O3 was dissolved in 40mL of methanol and ultrasonicated for 30min. Subsequently, 1.93mmol of HPtCl6·6H2O was added and stirring continued for 1h. After stirring, 10mL of NaBH4 (0.1M) aqueous solution was added and stirred vigorously for 1h. Finally, the product was collected by centrifugation, washed three times with ethanol, and dried to obtain a Pt / In2O3 supported catalyst (catalyst number C).

[0049] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 75%, and the aromatic selectivity was 67%.

[0050] Example 4

[0051] Dissolve 2g of indium nitrate and 1g of terephthalic acid (H2BDC) in 5mL of N,N-dimethylformamide (DMF), add 0.1mol of polyvinylpyrrolidone (PVP) and stir for 15min. Finally, transfer the obtained mixed solution to a 100mL autoclave with a polytetrafluoroethylene liner and react at 100℃ for 24h. After the reaction, centrifuge the obtained solution to obtain a white precipitate, wash it twice with ethanol, dry it at 60℃ overnight to obtain the product MIL-68 (In), and heat it to 500℃ at a rate of 10℃ / min, and calcine it at 500℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the catalyst was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number D).

[0052] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 70%, and the aromatic selectivity was 50%.

[0053] Example 5

[0054] 2g of indium nitrate and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mol of hexadecyltrimethylammonium chloride (CTAC) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100℃ for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60℃ overnight to obtain the product MIL-68 (In) and heated to 500℃ at a rate of 10℃ / min, and calcined at 500℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number E).

[0055] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 90%, and the aromatic selectivity was 72%.

[0056] Example 6

[0057] 2g of indium nitrate and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mL of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100℃ for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60℃ overnight to obtain the product MIL-68 (In) and heated to 400℃ at a rate of 10℃ / min, and calcined at 400℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number F).

[0058] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 94%, the deoxygenation rate was 80%, and the aromatic selectivity was 70%.

[0059] Example 7

[0060] 2g of indium nitrate and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mL of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100℃ for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60℃ overnight to obtain the product MIL-68 (In) and heated to 600℃ at a rate of 10℃ / min, and calcined at 600℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number F).

[0061] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 87%, and the aromatic selectivity was 65%.

[0062] Example 8

[0063] Dissolve 2g of indium iodide and 1g of terephthalic acid (H2BDC) in 5mL of N,N-dimethylformamide (DMF), add 0.1mol of triethanolamine (TEOA) and stir for 15min. Finally, transfer the obtained mixed solution to a 100mL autoclave with a polytetrafluoroethylene liner and react at 100℃ for 24h. After the reaction, centrifuge the obtained solution to obtain a white precipitate, wash it twice with ethanol, dry it at 60℃ overnight to obtain the product MIL-68 (In), and heat it to 400℃ at a rate of 10℃ / min, and calcine it at 400℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number G).

[0064] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 87%, the deoxygenation rate was 82%, and the aromatic selectivity was 63%.

[0065] Example 9

[0066] 2g of indium iodide and 1g of terephthalic acid (H2BDC) were dissolved in 5mL of N,N-dimethylformamide (DMF), and 0.1mol of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100℃ for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60℃ overnight to obtain the product MIL-68 (In) and heated to 600℃ at a rate of 10℃ / min, and calcined at 600℃ for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number H).

[0067] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 70%, and the aromatic selectivity was 50%.

[0068] Example 10

[0069] 2g of indium chloride and 1g of terephthalic acid H2BDC were dissolved in 5m of LN, N-dimethylformamide (DMF), and 0.1mol of triethanolamine (TEOA) was added and stirred for 15min. Finally, the obtained mixed solution was transferred to a 100mL autoclave with a polytetrafluoroethylene liner and reacted at 100°C for 24h. After the reaction, the obtained solution was centrifuged to obtain a white precipitate, which was washed twice with ethanol and dried at 60°C overnight to obtain the product MIL-68 (In) and heated to 600°C at a rate of 10°C / min, and calcined at 600°C for 2h. 200 mg of calcined In2O3 was dissolved in 40 mL of methanol and ultrasonicated for 30 min. After the ultrasonication, 1.93 mmol of HPtCl6·6H2O was added and stirring was continued for 1 h. After the stirring, 10 mL of NaBH4 (0.1 M) was added to reduce PtNPS and stirring was continued for 1 h. After the reaction, centrifugation was performed and the mixture was washed three times with ethanol and dried at 60 °C for 12 h to obtain a Pt / In2O3 supported catalyst (catalyst number I).

[0070] 0.5 mg of solid stearic acid sample was placed in a sample cup, and 20 mg of catalyst was placed in a 10 mL quartz tube in a secondary reactor. After the reaction was completed, GC-MS was used for analysis. The product conversion rate was 100%, the deoxygenation rate was 78%, and the aromatic selectivity was 75%.

[0071] It should be noted that the specific parameters or some commonly used reagents in the above embodiments are specific embodiments or preferred embodiments of the present invention, rather than limiting them; those skilled in the art can make adaptive adjustments within the scope of the present invention. In addition, unless otherwise specified, the raw materials used can also be conventional commercial products in the art, or prepared by conventional methods in the art.

[0072] The metal loading of the catalyst in the above examples of the present invention was detected by inductively coupled plasma mass spectrometry (ICP-OES, Agilent, 5100SVDV).

[0073] The particle size of the catalyst was analyzed by scanning electron microscopy (SEM, ZEISSSigma). The sample was dried overnight in an oven, the conductive glue was glued to the sample stage, a small amount of sample was applied to the conductive glue and purged with an ear bulb, the sample stage was transferred to a platinum sprayer, platinum was sprayed at 30 mA for 30 seconds, and then the sample stage was transferred to the sample chamber and evacuated for subsequent analysis. The instrument operating voltage was 15 kV, and observation was performed from high to low magnification.

[0074] The Pt / In2O3 supported catalyst prepared in the above-mentioned embodiment is used for non-hydrogenation catalytic deoxygenation of fatty acids, comprising the following steps: adding the Pt / In2O3 supported catalyst into a catalytic tube for catalytic reaction, the reaction temperature is 360-420°C, and the reaction time is 0.3-2min.

[0075] The fatty acid deoxygenation occurs in a Frontier continuous reactor (Py-GCMS) with a maximum pressure resistance of 68 MPa and a maximum temperature resistance of 800°C.

[0076] The mass ratio of the fatty acid to the Pt / In2O3 supported catalyst is 1:(60-1), preferably 1:40.

[0077] The reaction temperature of the fatty acid and the Pt / In2O3 supported catalyst is 360-420°C, preferably 380°C, and the reaction time is 0.3-2 min, preferably 1 min.

[0078] The Pt / In2O3 supported catalyst of the present invention is suitable for the catalytic dehydrogenation of various fatty acids. For example, in some embodiments, the fatty acids may include stearic acid, lauric acid or myristic acid, etc., and stearic acid is used in the embodiments of the present invention.

[0079] The catalytic cracking and deoxygenation experiment of stearic acid was carried out on the Frontier instrument-GCMS coupling device. Specifically, in general, 0.5 mg of solid stearic acid sample was taken and placed in a sample cup, and the catalyst was placed in a 10 mL quartz tube in the secondary reactor. The chromatographic column program was set on the GCMS coupling operating system (50 ° C for 4 minutes, then heated to 280 ° C at a rate of 10 ° C / min, and finally kept at 280 ° C for 4 minutes). In general, the vaporization temperature of the primary reactor was set to 380 ° C and the cracking temperature of the secondary reactor was set to 400 ° C on the Frontier instrument software. Under the initial conditions of a carrier gas pressure of 7.65 psi and a flow rate of 101.2 mL / min. When the reaction pressure was within the normal initial range, 0.5 mg of stearic acid was injected into the primary reactor and cracked for 2 minutes. After the cracking reaction was completed, the gas product obtained by cracking was cooled to a liquid state by a GC with liquid nitrogen, and the obtained liquid product was injected into the GCMS for analysis (fractionation ratio of 100:1). In addition, the products were qualitatively analyzed by MS results, and the GC spectrum results were further normalized by area method and correction factors were calculated for the components, and finally the conversion rate and selectivity of the reaction were calculated.

[0080] The characteristics of the catalyst in the embodiment of the present invention are detected by powder X-ray diffraction, the test range is 10°-90°, the radiation source is CuKα (λ=0.15418nm), the test tube voltage is 35KV, the current is 15mA and the corresponding scanning rate is 10° / min.

[0081] Please continue to refer to the attached figure. Figure 3 It can be proved that Pt is successfully loaded. Figure 4 This proves that Pt loading improves the selectivity of aromatics. Figure 5 It is the performance test of Pt / In2O3 for different carbon chain substrates;

[0082] in, Figure 4 , Figure 5 The left figure is the result diagram of conversion rate and deoxygenation efficiency, and the right figure is the distribution diagram of the generated products, including four products: alkanes, olefins, aromatics and ketones.

[0083] In addition, those skilled in the art should understand that, although there are many problems in the prior art, each embodiment or technical solution of the present invention can be improved in only one or several aspects, without having to solve all the technical problems listed in the prior art or background technology at the same time. Those skilled in the art should understand that the content not mentioned in a claim should not be used as a limitation on the claim.

[0084] Although the terms such as active ingredient, soluble salt, surfactant, solvent, supported type, etc. are used more frequently in this article, the possibility of using other terms is not excluded. These terms are used only to more conveniently describe and explain the essence of the present invention; interpreting them as any additional limitation is contrary to the spirit of the present invention;

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Application of an indium metal organic framework-derived Pt / In2O3 supported catalyst in non-hydrogenation catalytic deoxygenation of fatty acids, characterized in that: The Pt / In2O3 supported catalyst is composed of a Pt NPs active component and an In2O3 carrier, and its preparation method comprises the following steps: (1)In 3+ The soluble salt, terephthalic acid, surfactant and solvent are stirred and mixed uniformly to obtain a mixed solution; (2) placing the mixed solution in a reaction kettle and reacting at 80-110° C. for 15-25 hours; (3) The product obtained in step (2) is centrifuged, washed and dried to obtain a MIL-68 (In) metal organic framework, which is then calcined to obtain an In2O3 carrier; (4) Dispersing the In2O3 carrier obtained in step (3) in a solution containing a Pt metal precursor, and then adding a reducing agent for reduction to obtain a Pt / In2O3 supported catalyst.

2. The use according to claim 1, characterized in that: The content of Pt is 2wt%-3wt%.

3. The use according to claim 1, characterized in that: The surfactant and In 3+ The molar ratio of the soluble salt is 0-1:1, and the amount of the surfactant is not 0.

4. The use according to claim 1, characterized in that: In 3+ The soluble salt is a combination of one or more of indium nitrate, indium iodide and indium chloride.

5. The use according to claim 1, characterized in that: The surfactant is a combination of one or more of polyvinyl pyrrolidone, triethanolamine, and hexadecyltrimethylammonium chloride.

6. The use according to claim 1, characterized in that: The reducing agent is a combination of one or more of sodium borohydride, lithium aluminum hydride and potassium borohydride.

7. The use according to claim 1, characterized in that: In step (3), the calcination conditions are: calcination at 400-600° C. for 2-10 hours in an air atmosphere.

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