A molecular sieve catalyst for biomass oil hydrogenation to produce green aviation kerosene and its preparation method and application

Abstract

The present application relates to the technical field of biomass oil hydrogenation catalysts, and specifically discloses a molecular sieve catalyst for biomass oil hydrogenation to produce green aviation kerosene, and its preparation method and application. The molecular sieve catalyst includes the following components: ZSM-5 molecular sieve repaired with organophosphorus; precious metal component Ag, with a loading of 1~2wt%; non-precious metal additive Sn, with a loading of 6~10wt%; non-precious metal additive Cr, with a loading of 5~8wt%. The loading amount is the mass ratio of each element relative to the ZSM-5 molecular sieve raw material that has not been repaired by organophosphorus. The catalyst uses silver as the active center, which significantly reduces the material cost compared to the solution using platinum and palladium as the active center. Among them, the organophosphorus is bonded to the skeleton aluminum of the ZSM-5 molecular sieve, which significantly improves the hydrothermal stability and anti-carbon deposition ability of the molecular sieve. The ZSM-5 molecular sieve provides an acid center, providing H + The oxygen-containing groups in the protonated biomass oil, Sn and Cr cooperate with Ag to promote the dissociation of hydrogen into hydrogen atoms, and together complete the hydrogenation of the biomass oil.

Description

Technical Field

[0001] The present application relates to the technical field of biomass oil hydrogenation catalysts, and specifically to a molecular sieve catalyst for producing green aviation kerosene by hydrogenating biomass oil, and a preparation method and application thereof. Background Art

[0002] Biomass oil is a renewable energy source. However, directly using biomass oil as fuel has problems such as high viscosity and instability, and its quality needs to be improved through hydrogenation.

[0003] Hydrogenation catalysts in related technologies, such as metal sulfide catalysts, exhibit low activity and poor stability during the processing of biomass oil. Especially when faced with biomass raw materials containing high oxygen content, they are prone to carbon deposition and deactivation, which in turn limits the effective conversion of biomass oil into high-quality aviation kerosene.

[0004] Transition metal sulfide catalysts, when processing biomass raw materials with high oxygen content, are prone to passivation of active centers due to the influence of oxides, thereby reducing catalytic efficiency. Therefore, these catalysts often need to work under high temperature and high pressure, increasing energy consumption and cost.

[0005] Molecular sieve catalysts based on precious metals exhibit good catalytic activity in the catalysis of biomass oil, but the precious metals used in such catalysts are generally expensive precious metals such as platinum and palladium, which increases production costs. Summary of the Invention

[0006] In order to solve the problem of high cost of precious metal molecular sieve catalysts, the present application provides a relatively low-cost molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, as well as a preparation method and application thereof.

[0007] In the first aspect, the present application proposes a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, and adopts the following technical solution.

[0008] A molecular sieve catalyst for hydrogenating biooil to green aviation kerosene comprises the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1-2 wt %; a non-precious metal additive, Sn, at a loading of 6-10 wt %; and a non-precious metal additive, Cr, at a loading of 5-8 wt %. The loadings are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material without the organophosphorus repair.

[0009] By adopting the above technical solution, the catalyst uses silver as the active center, which significantly reduces the material cost compared to the solution using platinum and palladium as the active center. Among them, the organic phosphorus is bonded to the aluminum skeleton of the ZSM-5 molecular sieve, which significantly improves the hydrothermal stability and anti-carbon deposition ability of the molecular sieve. The ZSM-5 molecular sieve provides acid centers, providing H+ By protonating oxygen-containing groups (such as -OH and C=O) in biooil, Sn and Cr, in combination with Ag, promote the dissociation of hydrogen into hydrogen atoms. These hydrogen atoms attack the protonated oxygen-containing groups, dehydrating them to form olefinic bonds. Hydrogen atoms then add to these olefinic bonds, completing the hydrogenation of the biooil. Sn and Cr promote C-C bond isomerization, improving isomerization selectivity (the molecular sieve pores regulate hydrocarbon branching).

[0010] Secondly, the present application proposes a method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, and adopts the following technical solution.

[0011] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0012] Fluoride activation: Immerse the ZSM-5 molecular sieve in NH4F solution and treat at room temperature for 1 to 3 hours to obtain a mixed solution.

[0013] Organophosphorus coupling: adding a small molecule organophosphorus compound to the mixed solution, reacting at 50-70° C. for 2-4 hours to obtain a repair solution.

[0014] Metal loading: filtering the repair solution to obtain the organophosphorus repaired ZSM-5 molecular sieve, dripping a noble metal salt solution and a non-noble metal salt solution into the organophosphorus repaired ZSM-5 molecular sieve, and calcining at 400-500° C. for 3-5 hours to obtain the molecular sieve catalyst.

[0015] By adopting the above technical solution, NH4F activates the ZSM-5 molecular sieve, which is convenient for coupling with organic phosphorus. The noble metal salt solution and the non-noble metal salt solution are dripped into the ZSM-5 molecular sieve, and the metal molecules obtained by calcination are attached to the molecular sieve, becoming catalytic active centers.

[0016] A preferred embodiment of the method for preparing a molecular sieve catalyst for hydrogenating biooil to green aviation kerosene is as follows: the concentration of the NH4F solution is 5-10 g / L, and the volume ratio of the mass of the ZSM-5 molecular sieve to the NH4F solution is 30-50 g / L.

[0017] By adopting the above technical solution, NH4F fully activates the silanol bonds of the ZSM-5 molecular sieve.

[0018] A preferred embodiment of the method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene is that the small molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate added is 80-120 g / L.

[0019] By adopting the above technical solution, trimethyl phosphate increases the Brønsted acid sites of ZSM-5 molecular sieve (NH3-TPD confirms the acid content is 1.2 mmol / g).

[0020] A preferred embodiment of the method for preparing a molecular sieve catalyst for hydrogenating biooil to green aviation kerosene is that the noble metal salt solution is a silver nitrate solution, and the mass ratio of silver in the ZSM-5 molecular sieve to the silver nitrate solution is 100:(1-2).

[0021] By adopting the above technical solution, silver nitrate can generate silver molecules after calcination.

[0022] In a preferred embodiment of the method for preparing a molecular sieve catalyst for hydrogenating biooil to green aviation kerosene, the solutes in the non-precious metal salt solution are tin sulfate and chromium nitrate. The mass ratio of tin to chromium in the ZSM-5 molecular sieve and the non-precious metal salt solution is 100:(6-10):(5-8).

[0023] By adopting the above technical solution, tin and chromium are deposited on the molecular sieve in proportion.

[0024] Thirdly, the present application proposes the use of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, and adopts the following technical solution.

[0025] The invention discloses an application of a molecular sieve catalyst prepared by the above-mentioned preparation method for hydrogenating biomass oil to produce green aviation kerosene. The biomass oil and the molecular sieve catalyst are added to a reactor, heated to 200-210° C., and hydrogen is introduced. The reaction is carried out while maintaining a pressure of 8-12 MPa for 1-3 hours.

[0026] By adopting the above technical solution, under the reaction conditions, the biomass oil hydrogenation efficiency is high.

[0027] A preferred application of the molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene is a hydrogen-to-oil volume ratio of (700-900):1.

[0028] By adopting the above technical solution, the biomass oil is fully hydrogenated. The hydrogen-to-oil volume ratio represents the volume of standard hydrogen required per unit volume of raw oil.

[0029] In summary, the molecular sieve catalyst for biomass oil hydrogenation to produce green aviation kerosene and its preparation method and application in this application have the following beneficial effects: the cost of preparing the molecular sieve catalyst is relatively low, but when used to catalyze biomass oil hydrogenation, the hydrogenation efficiency and conversion rate are high. DETAILED DESCRIPTION

[0030] The following is a clear and complete description of the embodiments of the present application. Obviously, the embodiments described are only part of the embodiments of the present application, not all of the embodiments. Based on the following embodiments, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0031] Example 1

[0032] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0033] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 2 hours to obtain a mixed solution. The concentration of the NH4F solution is 8g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 40g / 1L.

[0034] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 60°C for 3 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 100g / L.

[0035] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 450°C for 4 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1.5 g of silver. The solutes in the non-noble metal salt solution were tin sulfate and chromium nitrate. The non-noble metal salt solution contained 8 g of tin and 6 g of chromium.

[0036] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1.5 wt %; a non-precious metal additive, Sn, at a loading of 8 wt %; and a non-precious metal additive, Cr, at a loading of 6 wt %. The loadings above are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0037] Example 2

[0038] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0039] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 1 hour to obtain a mixed solution. The concentration of the NH4F solution is 5g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 30g / 1L.

[0040] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 50°C for 4 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 80g / L.

[0041] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 400°C for 5 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1g of silver. The solutes in the non-noble metal salt solution were tin sulfate and chromium nitrate. The non-noble metal salt solution contained 6g of tin and 5g of chromium.

[0042] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1 wt %; a non-precious metal additive, Sn, at a loading of 6 wt %; and a non-precious metal additive, Cr, at a loading of 5 wt %. The loadings above are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0043] Example 3

[0044] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0045] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 3 hours to obtain a mixed solution. The concentration of the NH4F solution is 10g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 50g / L.

[0046] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 70°C for 2 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 120g / L.

[0047] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 500°C for 3 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 2g of silver. The solutes in the non-noble metal salt solution were tin sulfate and chromium nitrate. The non-noble metal salt solution contained 10g of tin and 8g of chromium.

[0048] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 2 wt %; a non-precious metal additive, Sn, at a loading of 10 wt %; and a non-precious metal additive, Cr, at a loading of 8 wt %. The loadings are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0049] Comparative Example 1

[0050] This comparative example prepares a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene. The difference from Example 1 is that the solute of the non-precious metal salt solution contains only tin sulfate and no chromium nitrate, as follows.

[0051] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0052] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 2 hours to obtain a mixed solution. The concentration of the NH4F solution is 8g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 40g / 1L.

[0053] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 60°C for 3 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 100g / L.

[0054] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 450°C for 4 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1.5 g of silver. The non-noble metal salt solution contained tin sulfate as the solute and 14 g of tin.

[0055] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1.5 wt %; and a non-precious metal additive, Sn, at a loading of 14 wt %. The loadings are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0056] Comparative Example 2

[0057] This comparative example prepares a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene. The difference from Example 1 is that the solute of the non-precious metal salt solution contains only chromium nitrate and no tin sulfate, as follows.

[0058] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0059] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 2 hours to obtain a mixed solution. The concentration of the NH4F solution is 8g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 40g / 1L.

[0060] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 60°C for 3 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 100g / L.

[0061] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 450°C for 4 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1.5 g of silver. The non-noble metal salt solution contained chromium nitrate as the solute, containing 14 g of chromium.

[0062] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1.5 wt %; and a non-precious metal additive, Cr, at a loading of 14 wt %. The loadings are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0063] Comparative Example 3

[0064] This comparative example prepares a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene. The difference from Example 1 is that NH4F is replaced by tetrabutylammonium fluoride, and trimethyl phosphate is replaced by tetraethylphosphine bromide, as follows.

[0065] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0066] Fluoride Activation: Immerse 100g of ZSM-5 molecular sieve in a tetrabutylammonium fluoride solution at room temperature (20-30°C) for 2 hours to obtain a mixed solution. The concentration of the tetrabutylammonium fluoride solution is 8g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the tetrabutylammonium fluoride solution is 40g / 1L.

[0067] Organophosphorus coupling: A small-molecule organophosphorus compound was added to the mixture and reacted at 60°C for 3 hours to obtain a repair solution. The small-molecule organophosphorus compound was tetraethylphosphine bromide (TEPB), and the initial concentration of TPB was 100 g / L.

[0068] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were then dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 450°C for 4 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1.5 g of silver. The solutes in the non-noble metal salt solution were tin sulfate and chromium nitrate. The non-noble metal salt solution contained 8 g of tin and 6 g of chromium.

[0069] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a precious metal component, Ag, at a loading of 1.5 wt %; a non-precious metal additive, Sn, at a loading of 8 wt %; and a non-precious metal additive, Cr, at a loading of 6 wt %. The loadings above are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0070] Comparative Example 4

[0071] This comparative example prepares a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene. The difference from Example 1 is that the non-precious metal additives Sn and Cr are replaced by Ni, as follows.

[0072] A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0073] Fluoride activation: Immerse 100g of ZSM-5 molecular sieve in an NH4F solution at room temperature (20-30°C) for 2 hours to obtain a mixed solution. The concentration of the NH4F solution is 8g / L, and the volume ratio of the ZSM-5 molecular sieve mass to the NH4F solution is 40g / 1L.

[0074] Organophosphorus coupling: A small-molecule organophosphorus compound is added to the mixture and reacted at 60°C for 3 hours to obtain a repair solution. The small-molecule organophosphorus compound is trimethyl phosphate, and the initial concentration of trimethyl phosphate is 100g / L.

[0075] Metal loading: The repair solution was filtered to obtain an organophosphorus-repaired ZSM-5 molecular sieve. A noble metal salt solution and a non-noble metal salt solution were dripped into the organophosphorus-repaired ZSM-5 molecular sieve. The mixture was calcined at 450°C for 4 hours to obtain a molecular sieve catalyst. The noble metal salt solution was a silver nitrate solution containing 1.5 g of silver. The solute in the non-noble metal salt solution was nickel nitrate, containing 14 g of nickel.

[0076] The molecular sieve catalyst prepared in this example includes the following components: an organophosphorus-repaired ZSM-5 molecular sieve; a 1.5 wt % loading of the precious metal Ag; and a 14 wt % loading of the non-precious metal Ni additive. The loadings are the mass ratios of each element relative to the raw material ZSM-5 molecular sieve without the organophosphorus repair.

[0077] Application Example 1

[0078] A reactor was charged with 1 L of soybean oil and 0.5 g of a molecular sieve catalyst. The reaction was heated to 200°C and hydrogen was introduced at a flow rate of 50 mL / min, with a hydrogen-to-oil volume ratio of 800:1. The reaction was maintained at a pressure of 10 MPa for 2 hours. After the reaction, the conversion rate, isomeric hydrocarbon ratio, carbon deposition rate, and 100-hour activity retention were measured using the following test methods.

[0079] 1) Determination of isomeric hydrocarbon ratio (GC×GC-TOFMS)

[0080] 1.1 Instruments

[0081] Comprehensive two-dimensional gas chromatography: Agilent 8890 + Zoex ZX2.

[0082] Mass spectrometry: Pegasus BT TOFMS.

[0083] 1.2 Analysis process:

[0084] The hydrogenation products were selected and subjected to silica gel column deoxygenation, GC×GC separation, and TOFMS qualitative analysis in sequence. The isomeric hydrocarbon ratio was quantified by the area normalization method. The formula for isomeric hydrocarbon ratio is as follows: isomeric hydrocarbon ratio = isoparaffin peak area / total hydrocarbon peak area × 100%.

[0085] 2) Carbon deposition rate determination (TGA)

[0086] 2.1 Conditions:

[0087] Instrument: Netzsch STA 449 F5.

[0088] Procedure: Take the catalyst after the reaction and heat it to 150℃ in N2 atmosphere (to remove moisture) to obtain the dry weight m2. Then switch to air atmosphere, heat it to 800℃ (to charcoal) and keep it at this temperature for 30 minutes to obtain the residual weight m3. The carbon deposition rate = (m2-m3) / m2 * 100%.

[0089] 3) Acidity determination (NH3-TPD)

[0090] 3.1 Parameters:

[0091] Adsorption temperature: 100℃.

[0092] Heating rate: 10℃ / min.

[0093] Detection: TCD signal.

[0094] Calculation of acid amount: calculated amount = A × K / m (mmol / g). Where A is the desorption peak area and K is the NH3 molar correction factor.

[0095] The molecular sieve catalyst prepared in Example 1 is characterized as shown in Table 1 below.

[0096]

[0097] The catalytic reaction data tested according to the above method are shown in Table 2 below.

[0098]

[0099] In Table 2, the conversion and isohydrocarbon ratio are data from the first catalytic reaction. The carbon deposition rate is data from 100 hours of continuous catalysis. The 100-hour activity retention (%) is the conversion rate of soybean oil hydrogenation after 100 hours of continuous catalytic reaction over the molecular sieve catalyst divided by the conversion rate of the first catalytic soybean oil hydrogenation.

[0100] In summary, the molecular sieve catalysts prepared in Examples 1-3 have a high conversion rate for catalyzing the hydrogenation of biomass oil. For example, the catalyst in Example 1 catalyzes a soybean oil conversion rate of 97% (GC-MS confirms that C8-C16 hydrocarbons account for 85%), an isomerized hydrocarbon conversion rate of 78% (branching induced by the molecular sieve pores), and an ultra-low carbon deposition rate of only 0.3% after 100 hours.

[0101] The product of biomass oil hydrogenation catalyzed by the catalyst of the embodiment is of excellent quality, conforms to the ASTM D7566 standard, and has great industrial value.

[0102] Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments, or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, characterized in that: include: Fluoride activation: Immerse the ZSM-5 molecular sieve in NH4F solution and treat at room temperature for 1-3 hours to obtain a mixed solution; Organophosphorus coupling: adding a small molecule organophosphorus compound to the mixed solution, reacting at 50-70°C for 2-4 hours to obtain a repair solution; Metal loading: filtering the repair solution to obtain an organophosphorus-repaired ZSM-5 molecular sieve, dripping a noble metal salt solution and a non-noble metal salt solution into the organophosphorus-repaired ZSM-5 molecular sieve, and calcining at 400-500° C. for 3-5 hours to obtain a molecular sieve catalyst; The molecular sieve catalyst comprises the following components: ZSM-5 molecular sieve repaired with organophosphorus; Precious metal component Ag, loading amount 1~2wt%; Non-precious metal additive Sn, loading amount 6~10wt%; Non-precious metal additive Cr, loading amount 5~8wt%; The loading amount is the mass ratio of each element to the ZSM-5 molecular sieve raw material that has not been repaired by organic phosphorus.

2. The method for preparing a molecular sieve catalyst for producing green aviation kerosene by hydrogenating biomass oil according to claim 1, characterized in that: The concentration of the NH4F solution is 5-10 g / L; the volume ratio of the mass of the ZSM-5 molecular sieve to the NH4F solution is 30-50 g / 1L.

3. The method for preparing a molecular sieve catalyst for producing green aviation kerosene by hydrogenating biomass oil according to claim 1, characterized in that: The small molecule organic phosphorus compound is trimethyl phosphate; the initial concentration of the added trimethyl phosphate is 80-120 g / L.

4. The method for preparing a molecular sieve catalyst for producing green aviation kerosene by hydrogenating biomass oil according to claim 1, characterized in that: The noble metal salt solution is a silver nitrate solution; the mass ratio of silver in the ZSM-5 molecular sieve and the silver nitrate solution is 100:(1~2).

5. The method for preparing a molecular sieve catalyst for producing green aviation kerosene by hydrogenating biomass oil according to claim 1, characterized in that: The solutes of the non-precious metal salt solution are tin sulfate and chromium nitrate; the mass ratio of tin to chromium in the ZSM-5 molecular sieve and the non-precious metal salt solution is 100: (6-10): (5-8).

6. An application of a molecular sieve catalyst prepared by the preparation method according to any one of claims 1 to 5 for hydrogenating biomass oil to produce green aviation kerosene, characterized in that: Add biomass oil and the molecular sieve catalyst into the reactor, heat to 200-210° C., introduce hydrogen, maintain the pressure at 8-12 MPa, and react for 1-3 hours.

7. The use of the molecular sieve catalyst for hydrogenating biooil to produce green aviation kerosene according to claim 6, characterized in that: Hydrogen to oil volume ratio (700~900): 1.

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