Hydrodeoxygenation catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of catalysts, and particularly discloses a hydrodeoxygenation catalyst and a preparation method and application thereof. The catalyst contains a silicon-zirconium composite oxide carrier and a CuCo alloy loaded on the carrier, the molar ratio of silicon to zirconium in the silicon-zirconium composite oxide is (1-5): 1. The preparation method comprises the following steps: 1) preparing a precursor containing copper, cobalt, silicon and zirconium by adopting a sol-gel method; 2) roasting the precursor to obtain a copper oxide and a cobalt oxide which take the silicon-zirconium composite oxide as a carrier; and 3) carrying out reduction treatment on the material obtained in the step 2) to obtain the catalyst. The catalyst provided by the invention has high activity and alkane selectivity in hydrodeoxygenation reactions of various aldehyde ketone condensates, and can be used for hydrodeoxygenation reactions of aldehyde ketone condensation mixtures to produce aviation fuels.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a hydrodeoxygenation catalyst and its preparation method, and the application of the catalyst in the hydrodeoxygenation of aldehyde-ketone condensates to produce alkanes. Background Technology

[0002] Globalization has fueled the booming development of the aviation industry, but the aviation fuel upon which it relies is facing fundamental challenges. Currently, global energy consumption remains dominated by fossil fuels, which generate massive amounts of carbon dioxide, exacerbating the greenhouse effect. Faced with dwindling oil reserves and global warming, finding sustainable and environmentally friendly alternative energy sources has become an urgent priority. Utilizing renewable biomass to produce sustainable aviation fuel is considered a key measure to replace traditional fossil fuels and achieve deep decarbonization of the aviation industry. The International Air Transport Association (IATA) has pledged to achieve net-zero carbon emissions for the aviation industry by 2050, highlighting the urgency and strategic significance of developing sustainable aviation fuel.

[0003] Among numerous sustainable aviation fuel production technologies, the route of producing liquid alkanes from biomass oil obtained through biomass pyrolysis, followed by condensation and hydrogenation of C5-C8 aldehydes and ketones from the biomass oil, has attracted considerable attention due to its wide availability of raw materials and low energy consumption. However, in the hydrodeoxygenation reaction of aldehyde-ketone condensation mixtures, the CO bond has a high bond energy and is difficult to break, and the ease of breaking different carbon-oxygen bonds (primary hydroxyl CO, secondary hydroxyl CO, furan cyclic ether COC) varies. Therefore, there is a need to develop highly efficient hydrodeoxygenation catalytic systems capable of activating different carbon-oxygen bonds. Summary of the Invention

[0004] In view of the above, the purpose of this invention is to provide a hydrodeoxygenation catalyst, its preparation method and application. By adjusting the acid / base support to regulate the type and density / strength of the acid, the synergistic effect of the metal and the acidic site is optimized, and a highly efficient metal-acid synergistic catalytic system is constructed. This enables selective hydrogenation of different types of carbon-oxygen bonds in mixed condensates and efficient deoxygenation of oxygen-containing intermediates, thereby improving the selectivity of the target alkane product.

[0005] A first aspect of the present invention provides a hydrodeoxygenation catalyst comprising a silicon-zirconium composite oxide support and a CuCo alloy supported on the support; wherein the molar ratio of silicon to zirconium in the silicon-zirconium composite oxide is 1-5:1.

[0006] A second aspect of the present invention provides a method for preparing the above-described hydrodeoxygenation catalyst, the method comprising the following steps:

[0007] 1) Precursors containing copper, cobalt, silicon, and zirconium were prepared using the sol-gel method;

[0008] 2) The precursor was calcined to obtain copper oxide and cobalt oxide with silicon-zirconium composite oxide as the support;

[0009] 3) The material obtained in step 2) is subjected to reduction treatment to obtain the catalyst.

[0010] A third aspect of the present invention provides the application of the above-described hydrodeoxygenation catalyst in the hydrodeoxygenation of aldehyde-ketone condensates to produce alkanes.

[0011] Compared with the prior art, the present invention has the following beneficial effects:

[0012] In the catalyst of this invention, the CuCo alloy can activate hydrogen gas, which is beneficial for the hydrogenation of C=C and C=O bonds; the silicon-zirconium composite oxide has... The acid sites or Lewis acid sites, in synergy with metals, promote C-OH activation, which helps to lower the C-OH breaking energy barrier and improve deoxygenation efficiency. The catalyst of this invention has high activity and alkane selectivity in the hydrodeoxygenation reaction of various aldehyde-ketone condensates, and can be used in the hydrodeoxygenation reaction of aldehyde-ketone condensate mixtures to produce aviation fuel.

[0013] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0014] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0015] According to a first aspect of the present invention, the present invention provides a hydrodeoxygenation catalyst comprising a silicon-zirconium composite oxide support and a CuCo alloy supported on the support; wherein the molar ratio of silicon to zirconium in the silicon-zirconium composite oxide is 1-5:1.

[0016] In this invention, the loading of Cu can be 4-18 wt%, preferably 5-16 wt%, and the loading of Co can be 3-16 wt%, preferably 4-15 wt%, based on the total weight of the catalyst.

[0017] According to the present invention, the particle size of CuCo alloy can be 3-10 nm, preferably 6-7 nm.

[0018] In a preferred embodiment, the molar ratio of silicon to zirconium in the silicon-zirconium composite oxide is 2-4:1. For example, the molar ratio of silicon to zirconium can be 2:1, 3:1, or 4:1.

[0019] According to a second aspect of the present invention, the present invention provides a method for preparing the above-described hydrodeoxygenation catalyst, the method comprising the following steps:

[0020] 1) Precursors containing copper, cobalt, silicon, and zirconium were prepared using the sol-gel method;

[0021] 2) The precursor was calcined to obtain copper oxide and cobalt oxide with silicon-zirconium composite oxide as the support;

[0022] 3) The material obtained in step 2) is subjected to reduction treatment to obtain the catalyst.

[0023] In this invention, the precursor containing copper, cobalt, silicon and zirconium can be prepared using conventional methods in the prior art, as long as the content of each element meets the composition of the catalyst.

[0024] Preferably, the sol-gel method includes:

[0025] (1) Dissolve the organosilicon compound in an organic solvent to prepare solution A;

[0026] (2) Dissolve copper salt, cobalt salt and zirconium salt in water to prepare solution B;

[0027] (3) Under stirring, solution B is added dropwise to solution A. After mixing evenly, the mixture is kept at a constant temperature to obtain a wet gel. After drying, a dry gel is obtained.

[0028] According to the present invention, the precursors for preparing each element in the catalyst can be conventionally selected according to existing technology. For example, the organosilicon compound can be tetraethyl silicate, the organic solvent can be anhydrous ethanol, the copper salt can be copper nitrate, the cobalt salt can be cobalt nitrate, and the zirconium salt can be zirconium oxynitrate.

[0029] Preferably, in step (3), the settling temperature is 50-80℃ and the settling time is 12-36 hours.

[0030] Preferably, in step (3), the drying temperature is 50-80℃.

[0031] In step 2) of the present invention, the calcination temperature can be 400-600℃, the calcination time is 2-6 hours, and the heating rate is 1-5℃ / min.

[0032] According to the present invention, in step 3), the reduction treatment includes: reducing the material in a hydrogen atmosphere at 550-650°C for 2-5 hours, with a heating rate of 5-10°C / min and a hydrogen flow rate of 10-60 mL / min / g, preferably 40 mL / min / g. Here, the / g in the hydrogen flow rate refers to each gram of raw material being reduced.

[0033] According to a third aspect of the present invention, the present invention provides the application of the above-described hydrodeoxygenation catalyst in the hydrodeoxygenation of aldehyde-ketone condensates to produce alkanes.

[0034] In this invention, the aldehyde-ketone condensate is selected from at least one of 2-cyclopentenecyclopentanone, 2-propylheptenal, 2-(2-furanmethyl)pentanal, and α,α′-difurfuralcyclopentanone.

[0035] According to the present invention, the reaction conditions for hydrodeoxygenation may include: a temperature of 160-240°C and a pressure of 3.5-4.5 MPa.

[0036] In addition, the solvent for the aldehyde-ketone condensation reaction can be cyclohexane, the concentration of the reaction solution can be 0.05-0.5 mol / L, and the amount of catalyst used can be 0.01-0.5 g.

[0037] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0038] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0039] Example 1

[0040] Step A: Weigh 8.239 g of tetraethyl orthosilicate and mix with 8.08 g of anhydrous ethanol. Stir at room temperature for about 30 min to prepare solution A. Weigh 2.905 g of Cu(NO3)2·3H2O, 1.166 g of Co(NO3)2·6H2O, and 3.045 g of ZrO(NO3)2 and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0041] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu3. II Co1 II -Si(Zr)O2-3(Cu3 II Co1 II In II This indicates that the metal originates from the corresponding divalent metal ion.

[0042] Step C: The Cu3 prepared in step B... II Co1 II-Si(Zr)O₂⁻⁃ was placed in a tube furnace and reduced at 600℃ for 4 h in a H₂ atmosphere with a heating rate of 10℃ / min and an H₂ flow rate of 40 mL / min / g to prepare the catalyst Cu₃Co₁-Si(Zr)O₂⁻⁃. The actual Cu loading was 15.39 wt%, and the actual Co loading was 4.64 wt%. The particle size of the CuCo alloy was 6.7 nm.

[0043] Example 2

[0044] Step A: Weigh 8.239 g of tetraethyl silicate and 8.08 g of anhydrous ethanol, mix them, and stir at room temperature for about 30 min to prepare solution A. Weigh 1.973 g of Cu(NO3)2·3H2O, 2.376 g of Co(NO3)2·6H2O, and 3.045 g of ZrO(NO3)2 and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0045] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu1. II Co1 II -Si(Zr)O2-3.

[0046] Step C: The Cu1 prepared in step B... II Co1 II -Si(Zr)O₂⁻⁃ was placed in a tube furnace and reduced at 600℃ for 4 h in a H₂ atmosphere with a heating rate of 10℃ / min and an H₂ flow rate of 40 mL / min / g to prepare the catalyst Cu₁Co₁-Si(Zr)O₂⁻⁃. The actual Cu loading was 10.52 wt%, and the actual Co loading was 9.43 wt%. The particle size of the CuCo alloy was 6.5 nm.

[0047] Example 3

[0048] Step A: Weigh 8.239 g of tetraethyl orthosilicate and mix with 8.08 g of anhydrous ethanol. Stir at room temperature for about 30 min to prepare solution A. Weigh 1.005 g of Cu(NO3)2·3H2O, 3.632 g of Co(NO3)2·6H2O, and 3.045 g of ZrO(NO3)2 and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0049] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu1. II Co3 II -Si(Zr)O2-3.

[0050] Step C: The Cu1 prepared in step B... II Co3 II -Si(Zr)O₂⁻⁃ was placed in a tube furnace and reduced at 600℃ for 4 h in a H₂ atmosphere with a heating rate of 10℃ / min and an H₂ flow rate of 40 mL / min / g to prepare the catalyst Cu₁Co₃-Si(Zr)O₂⁻⁃. The actual Cu loading was 5.19 wt%, and the actual Co loading was 14.66 wt%. The particle size of the CuCo alloy was 6.4 nm.

[0051] Example 4

[0052] Step A: Weigh 7.317 g of tetraethyl silicate and 8.08 g of anhydrous ethanol, mix them, and stir at room temperature for about 30 min to prepare solution A. Weigh 2.905 g of Cu(NO3)2·3H2O, 1.166 g of Co(NO3)2·6H2O, and 4.061 g of ZrO(NO3)2 and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0053] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu3. II Co1 II-Si(Zr)O2-2.

[0054] Step C: The Cu3 prepared in step B... II Co1 II -Si(Zr)O2-2 was placed in a tube furnace and reduced at 600℃ for 4 h in a H2 atmosphere with a heating rate of 10℃ / min and an H2 flow rate of 40 mL / min / g to prepare the catalyst Cu3Co1-Si(Zr)O2-2. The actual Cu loading was 15.46 wt%, and the actual Co loading was 4.73 wt%. The particle size of the CuCo alloy was 6.7 nm.

[0055] Example 5

[0056] Step A: Weigh 8.779 g of tetraethyl silicate and 8.08 g of anhydrous ethanol, mix them, and stir at room temperature for about 30 min to prepare solution A. Weigh 2.905 g of Cu(NO3)2·3H2O, 1.166 g of Co(NO3)2·6H2O, and 2.437 g of ZrO(NO3)2 and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0057] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu3. II Co1 II -Si(Zr)O2-4.

[0058] Step C: The Cu3 prepared in step B... II Co1 II -Si(Zr)O₂⁻⁴ was placed in a tube furnace and reduced at 600℃ for 4 h in a H₂ atmosphere with a heating rate of 10℃ / min and an H₂ flow rate of 40 mL / min / g to prepare the catalyst Cu₃Co₁-Si(Zr)O₂⁻⁴. The actual Cu loading was 15.29 wt%, and the actual Co loading was 4.73 wt%. The particle size of the CuCo alloy was 6.5 nm.

[0059] Comparative Example 1

[0060] Step A: Weigh 13.860 g of tetraethyl orthosilicate and mix with 15.5 g of anhydrous ethanol. Stir at room temperature for about 30 min to prepare solution A. Weigh 2.905 g of Cu(NO3)2·3H2O and 1.166 g of Co(NO3)2·6H2O and dissolve them in a beaker containing 35 mL of deionized water. Stir until all the reagents are completely dissolved to obtain a clear solution B. Slowly add solution B dropwise to solution A under vigorous stirring to obtain a clear and transparent mixed solution. Stir at room temperature for 30 min. Then place the mixed solution in a 60°C water bath and let it stand for 24 h to obtain a wet gel. Place the wet gel in a 60°C forced-air drying oven to dry to obtain a dry gel.

[0061] Step B: The dry gel prepared in Step A was placed in a muffle furnace and calcined at 500℃ for 4 hours at a heating rate of 2℃ / min to obtain Cu3. II Co1 II -SiO2.

[0062] Step C: The Cu3 prepared in step B... II Co1 II -SiO2 was placed in a tube furnace and reduced at 600℃ for 4 h in an H2 atmosphere with a heating rate of 10℃ / min and an H2 flow rate of 40 mL / min / g to prepare the catalyst Cu3Co1-SiO2. The actual Cu loading was 15.36 wt%, and the actual Co loading was 4.78 wt%. The particle size of the CuCo alloy was 6.3 nm.

[0063] Comparative Example 2

[0064] Step A: Weigh 2.905g of Cu(NO3)2·3H2O, 1.166g of Co(NO3)2·6H2O, and 7.505g of ZrO(NO3)2 and dissolve them in a beaker containing 100mL of deionized water. Stir until all reagents are completely dissolved to obtain a clear solution A. Weigh 10.409g of sodium carbonate and dissolve it in a beaker containing 100mL of deionized water. Stir until all reagents are completely dissolved to obtain a clear solution B. Place a four-necked round-bottom flask containing 150mL of deionized water in a water bath at 25℃ and stir rapidly using a mechanical stirrer. Simultaneously add solutions A and B dropwise to the four-necked flask, maintaining the pH of the system at 10. After the solutions have been added, crystallize in a constant temperature water bath at 30℃ for 12 hours. The resulting suspension is filtered under reduced pressure, washed repeatedly with deionized water until neutral, and the resulting filter cake is dried overnight in a 60℃ oven. The dried solid was ground into powder to obtain CuCoZr-MH (mixed hydroxide).

[0065] Step B: The CuCoZr-MH prepared in Step A was placed in a tube furnace and reduced at 600℃ for 4 h in an H2 atmosphere with a heating rate of 10℃ / min and an H2 flow rate of 40 mL / min / g to prepare the catalyst Cu3Co1-ZrO2. The actual Cu loading was 15.19 wt%, and the actual Co loading was 4.67 wt%. The particle size of the CuCo alloy was 6.3 nm.

[0066] Comparative Example 3

[0067] Step A: Weigh 2.905g of Cu(NO3)2·3H2O, 1.166g of Co(NO3)2·6H2O, 14.502g of Mg(NO3)2·6H2O, and 10.603g of Al(NO3)3·9H2O and dissolve them in a beaker containing 100mL of deionized water. Stir until all reagents are completely dissolved to obtain a clear solution A. Weigh 8.070g of NaOH and 1.700g of Na2CO3 and dissolve them in a beaker containing 100mL of deionized water. Stir until all reagents are completely dissolved to obtain a clear solution B. Place a four-necked round-bottom flask containing 150mL of deionized water in a water bath at 25℃. Stir rapidly using a mechanical stirrer. Simultaneously add solutions A and B dropwise to the four-necked flask, controlling the pH of the system to 9.5±0.2. After the solutions have been added, crystallize in a constant temperature water bath at 30℃ for 12 hours. The obtained suspension was filtered under reduced pressure and repeatedly washed with deionized water until neutral. The resulting filter cake was then dried overnight in an oven at 60°C. The dried solid was ground into powder to obtain CuCoMgAl-LDHs (layered double hydroxides).

[0068] Step B: The CuCoMgAl-LDHs prepared in Step A were placed in a tube furnace and reduced at 600℃ for 4 h in an H2 atmosphere with a heating rate of 10℃ / min and an H2 flow rate of 40 mL / min / g to prepare the catalyst Cu3Co1-Mg(Al)O. The actual Cu loading was 15.31 wt%, and the actual Co loading was 4.76 wt%. The particle size of the CuCo alloy was 6.5 nm.

[0069] The catalysts prepared in each example and comparative example were loaded into mechanically stirred tanks, and 2-cyclopentenecyclopentanone was added as a reactant. Cyclohexane was used as the solvent, and the concentration of the reaction solution was 0.13 mol / L. The reaction temperature was 200℃, the pressure of the reactor was 4.5 MPa, and the stirring speed was 300 rpm. The catalytic performance of the hydrodeoxygenation reaction in each example and comparative example is shown in Table 1.

[0070] Table 1

[0071] catalyst Conversion rate (%) Alkane selectivity (%) Example 1 [Cu3Co1-Si(Zr)O2-3] 99 100.0 Example 2 [Cu1Co1-Si(Zr)O2-3] 99 94.3 Example 3 <![CDATA[Cu1Co3-Si(Zr)O2-3]]> 99 90.8 Example 4 <![CDATA[Cu3Co1-Si(Zr)O2-2]]> 99 95.1 Example 5 <![CDATA[Cu3Co1-Si(Zr)O2-4]]> 99 87.3 Comparative Example 1 <![CDATA[Cu3Co1-ZrO2]]> 99 15.0 Comparative Example 2 <![CDATA[Cu3Co1-SiO2]]> 99 25.6 Comparative Example 3 <![CDATA[Cu3Co1-Mg(Al)O]]> 99 60.0

[0072] Note: Cu3Co1 indicates that the loading ratio of Cu to Co is approximately 3:1; Cu1Co1 indicates that the loading ratio of Cu to Co is approximately 1:1; Cu1Co3 indicates that the loading ratio of Cu to Co is approximately 1:3; Si(Zr)O2-3 indicates that the molar ratio of Si / Zr in the composite oxide is 3:1; Si(Zr)O2-2 indicates that the molar ratio of Si / Zr in the composite oxide is 2:1; Si(Zr)O2-4 indicates that the molar ratio of Si / Zr in the composite oxide is 4:1.

[0073] The catalysts prepared in each example and comparative example were loaded into mechanically stirred tanks, and 2-propylheptenal was added as a reactant. Cyclohexane was used as the solvent, and the concentration of the reaction solution was 0.13 mol / L. The reaction temperature was 200℃, the pressure of the reactor was 4.5 MPa, and the stirring speed was 300 rpm. The catalytic performance of the hydrodeoxygenation reaction in each example and comparative example is shown in Table 2.

[0074] Table 2

[0075] catalyst Conversion rate (%) Alkane selectivity (%) Example 1 <![CDATA[Cu3Co1-Si(Zr)O2-3]]> 99 100.0 Example 2 <![CDATA[Cu1Co1-Si(Zr)O2-3]]> 99 92.3 Example 3 <![CDATA[Cu1Co3-Si(Zr)O2-3]]> 99 87.9 Example 4 <![CDATA[Cu3Co1-Si(Zr)O2-2]]> 99 89.0 Example 5 <![CDATA[Cu3Co1-Si(Zr)O2-4]]> 99 83.2 Comparative Example 1 <![CDATA[Cu3Co1-ZrO2]]> 99 6.0 Comparative Example 2 <![CDATA[Cu3Co1-SiO2]]> 99 8.8 Comparative Example 3 <![CDATA[Cu3Co1-Mg(Al)O]]> 99 14.4

[0076] The catalysts prepared in each example and comparative example were loaded into mechanically stirred tanks, and 2-(2-furanmethyl)pentanal was added as a reactant. Cyclohexane was used as the solvent, and the concentration of the reaction solution was 0.13 mol / L. The reaction temperature was 200℃, the pressure of the reactor was 4.5 MPa, and the stirring speed was 300 rpm. The catalytic performance of the hydrodeoxygenation reaction in each example and comparative example is shown in Table 3.

[0077] Table 3

[0078] catalyst Conversion rate (%) Alkane selectivity (%) Example 1 <![CDATA[Cu3Co1-Si(Zr)O2-3]]> 99 82.3 Example 2 <![CDATA[Cu1Co1-Si(Zr)O2-3]]> 99 78.6 Example 3 <![CDATA[Cu1Co3-Si(Zr)O2-3]]> 99 67.9 Example 4 <![CDATA[Cu3Co1-Si(Zr)O2-2]]> 99 72.1 Example 5 <![CDATA[Cu3Co1-Si(Zr)O2-4]]> 99 59.3 Comparative Example 1 <![CDATA[Cu3Co1-ZrO2]]> 99 6.5 Comparative Example 2 <![CDATA[Cu3Co1-SiO2]]> 99 34.0 Comparative Example 3 <![CDATA[Cu3Co1-Mg(Al)O]]> 99 11.3

[0079] The catalysts prepared in each example and comparative example were loaded into mechanically stirred tanks, and the reactant α,α′-difurfuralcyclopentanone was added. Cyclohexane was used as the solvent, and the concentration of the reaction solution was 0.13 mol / L. The reaction temperature was 200℃, the pressure of the reactor was 4.5 MPa, and the stirring speed was 300 rpm. The catalytic performance of the hydrodeoxygenation reaction in each example and comparative example is shown in Table 4.

[0080] Table 4

[0081] catalyst Conversion rate (%) Alkane selectivity (%) Example 1 <![CDATA[Cu3Co1-Si(Zr)O2-3]]> 99 69.7 Example 2 <![CDATA[Cu1Co1-Si(Zr)O2-3]]> 99 63.8 Example 3 <![CDATA[Cu1Co3-Si(Zr)O2-3]]> 99 58.4 Example 4 <![CDATA[Cu3Co1-Si(Zr)O2-2]]> 99 60.0 Example 5 <![CDATA[Cu3Co1-Si(Zr)O2-4]]> 99 52.0 Comparative Example 1 <![CDATA[Cu3Co1-ZrO2]]> 99 13.8 Comparative Example 2 <![CDATA[Cu3Co1-SiO2]]> 99 31.1 Comparative Example 3 <![CDATA[Cu3Co1-Mg(Al)O]]> 99 44.7

[0082] The catalysts prepared in Example 1 and Comparative Examples 1-3 were respectively loaded into mechanically stirred tanks, and a mixed reactant (2-cyclopentenecyclopentanone: 2-propylheptenal: 2-(2-furanmethyl)pentanal: α,α′-difurfuralcyclopentanone in a molar ratio of 1∶1∶1∶1) was added. Cyclohexane was used as the solvent, and the total concentration of the reaction solution was 0.13 mol / L. The reaction temperature was 200℃, the tank pressure was 4.5 MPa, and the stirring speed was 300 rpm. The catalytic performance of the hydrodeoxygenation reaction in Example 1 and Comparative Examples 1-3 is shown in Table 5.

[0083] Table 5

[0084]

[0085] Note: Overall conversion = total molar amount of reactants converted / total molar amount of reactants added × 100%; Overall alkane selectivity = total molar amount of alkanes produced / total molar amount of products × 100%.

[0086] As shown in Tables 1, 2, 3, 4, and 5, compared with the comparative example, the catalyst of the present invention has higher specific activity and higher alkane selectivity. This is because the composite oxide possesses... The acid sites, or Lewis acid sites, synergistically promote C-OH activation with metal CuCo, which helps to lower the C-OH breaking energy barrier and improve deoxygenation efficiency. In particular, the Cu3Co1-Si(Zr)O2-3 catalyst exhibits high alkane selectivity in the hydrodeoxygenation reactions of four aldehyde-ketone condensates and their mixtures.

[0087] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A hydrodeoxygenation catalyst, characterized in that, The catalyst contains a silicon-zirconium composite oxide support and a CuCo alloy supported on the support; the molar ratio of silicon to zirconium in the silicon-zirconium composite oxide is 1-5:

1.

2. The hydrodeoxygenation catalyst according to claim 1, wherein, The loading of Cu is 4-18 wt% and the loading of Co is 3-16 wt% based on the total weight of the catalyst.

3. The hydrodeoxygenation catalyst according to claim 1, wherein, The particle size of CuCo alloy is 3-10 nm.

4. The method for preparing the hydrodeoxygenation catalyst according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: 1) Precursors containing copper, cobalt, silicon, and zirconium were prepared using the sol-gel method; 2) The precursor was calcined to obtain copper oxide and cobalt oxide with silicon-zirconium composite oxide as the support; 3) The material obtained in step 2) is subjected to reduction treatment to obtain the catalyst.

5. The method for preparing the hydrodeoxygenation catalyst according to claim 4, wherein, The sol-gel method includes: (1) Dissolve the organosilicon compound in an organic solvent to prepare solution A; (2) Dissolve copper salt, cobalt salt and zirconium salt in water to prepare solution B; (3) Under stirring, solution B is added dropwise to solution A, mixed evenly, and then kept at a constant temperature to obtain a wet gel. After drying, a dry gel is obtained. Preferably, in step (3), the standing temperature is 50-80℃ and the standing time is 12-36 hours; the drying temperature is 50-80℃.

6. The method for preparing the hydrodeoxygenation catalyst according to claim 5, wherein, In step 2), the calcination temperature is 400-600℃, the calcination time is 2-6 hours, and the heating rate is 1-5℃ / min.

7. The method for preparing the hydrodeoxygenation catalyst according to claim 5, wherein, In step 3), the reduction treatment includes: reducing at 550-650℃ for 2-5 hours in a hydrogen atmosphere, with a heating rate of 5-10℃ / min and a hydrogen flow rate of 10-60mL / min / g.

8. The application of the hydrodeoxygenation catalyst according to any one of claims 1-3 in the hydrodeoxygenation of aldehyde-ketone condensates to produce alkanes.

9. The application of the hydrodeoxygenation catalyst according to claim 8 in the hydrodeoxygenation of aldehyde-ketone condensates to alkanes, wherein, The aldehyde-ketone condensate is selected from at least one of 2-cyclopentenecyclopentanone, 2-propylheptenal, 2-(2-furanmethyl)pentanal, and α,α′-difuronylcyclopentanone.

10. The application of the hydrodeoxygenation catalyst according to claim 8 in the hydrodeoxygenation of aldehyde-ketone condensates to alkanes, wherein, The reaction conditions for hydrodeoxygenation include a temperature of 160-240℃ and a pressure of 3.5-4.5MPa.

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