Molecular sieve catalyst for preparing green aviation kerosene through hydrogenation of biomass oil as well as preparation method and application of molecular sieve catalyst

Abstract

The invention relates to the technical field of biomass oil hydrogenation catalysts, and particularly discloses a molecular sieve catalyst for preparing green aviation kerosene through biomass oil hydrogenation as well as a preparation method and application of the molecular sieve catalyst. The molecular sieve catalyst comprises the following components: an organic phosphorus repaired ZSM-5 molecular sieve; the loading capacity of the noble metal component Ag is 1-2wt%; the loading capacity of the non-noble metal auxiliary agent Sn is 6-10 wt%; and the loading capacity of the non-noble metal auxiliary agent Cr is 5-8 wt%. The loading capacity is the mass ratio of each element to the ZSM-5 molecular sieve raw material which is not repaired by the organic phosphorus. The catalyst takes silver as an active center, and compared with a scheme adopting platinum and palladium as active centers, the catalyst has the advantage that the material cost is remarkably reduced. Wherein the organic phosphorus is bonded with framework aluminum of the ZSM-5 molecular sieve, so that the hydrothermal stability and the carbon deposition resistance of the molecular sieve are remarkably improved. The ZSM-5 molecular sieve provides an acid center and provides H < + > to protonate oxygen-containing groups in the biomass oil, and Sn and Cr are matched with Ag to promote hydrogen to be dissociated into hydrogen atoms, so that the hydrogenation effect on the biomass oil is jointly completed.

Description

Technical Field

[0001] This application relates to the technical field of biomass oil hydrogenation catalysts, and specifically relates to a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, its preparation method and application. 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 hydrotreatment.

[0003] Hydrogenation catalysts in related technologies, such as metal sulfide catalysts, show low activity and poor stability during the processing of biomass oil. Especially when facing biomass raw materials with a high oxygen content, carbon deposition deactivation is likely to occur, thereby restricting the effective conversion of biomass oil into high-quality aviation kerosene.

[0004] Based on transition metal sulfide catalysts, when dealing with biomass raw materials with a high oxygen content, the active centers are easily passivated due to the influence of oxides, thus reducing the catalytic efficiency. Therefore, these catalysts often need to work under high temperature and high pressure, increasing energy consumption and costs.

[0005] Molecular sieve catalysts based on noble metals show good catalytic activity when catalyzing biomass oil, but the noble metals used in such catalysts are generally expensive noble metals such as platinum and palladium, increasing production costs. Summary of the Invention

[0006] In order to solve the problem of high cost of noble metal molecular sieve catalysts, this application provides a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene with relatively low cost, its preparation method and application.

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

[0008] A molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, comprising the following components: organophosphorus-repaired ZSM-5 molecular sieve; noble metal component Ag, with a loading amount of 1-2 wt%; non-noble metal promoter Sn, with a loading amount of 6-10 wt%; non-noble metal promoter Cr, with a loading amount of 5-8 wt%. The loading amount is the mass ratio of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0009] By adopting the above technical solutions, this catalyst uses silver as the active center, and significantly reduces the material cost compared with the solution using platinum and palladium as the active center. Among them, organophosphorus bonds with the framework aluminum of the ZSM-5 molecular sieve, significantly improving the hydrothermal stability and anti-carbon deposition ability of the molecular sieve. The ZSM-5 molecular sieve provides acid centers to provide H+ In protonated bio-oil, for oxygen-containing groups (such as -OH, C=O), Sn and Cr cooperate with Ag to promote the dissociation of hydrogen into hydrogen atoms. The hydrogen atoms attack the protonated oxygen-containing groups, dehydrate to form double bonds, and the hydrogen atoms are added to the double bonds, completing the hydrogenation of bio-oil. Sn and Cr promote the isomerization of C-C bonds and improve the isomerization selectivity (the pore channels of molecular sieves regulate the branching of hydrocarbons).

[0010] Second, the present application proposes a preparation method of a molecular sieve catalyst for the hydrogenation of bio-oil to green aviation kerosene, and adopts the following technical solutions.

[0011] A preparation method of a molecular sieve catalyst for the hydrogenation of bio-oil to green aviation kerosene includes the following steps.

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

[0013] Organic phosphorus coupling: Add a small molecule organic phosphorus compound to the mixed solution and react at 50-70 °C for 2-4 h to obtain a repaired solution.

[0014] Metal loading: Filter the repaired solution to obtain the ZSM-5 molecular sieve repaired by organic phosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organic phosphorus and calcine it at 400-500 °C for 3-5 h to obtain the molecular sieve catalyst.

[0015] By adopting the above technical solutions, NH4F activates the ZSM-5 molecular sieve, facilitating the coupling of organic phosphorus. The noble metal salt solution and the non-noble metal salt solution are dropped into the ZSM-5 molecular sieve, and after calcination, metal molecules are attached to the molecular sieve to become catalytic active centers.

[0016] A preferred scheme of the preparation method of the molecular sieve catalyst for the hydrogenation of bio-oil to green aviation kerosene is that the concentration of the NH4F solution is 5-10 g / L. The mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 30-50 g / 1 L.

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

[0018] A preferred scheme of the preparation method of the molecular sieve catalyst for the hydrogenation of bio-oil to green aviation kerosene is that the small molecule organic phosphorus compound is trimethyl phosphate. 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 zeolite (the acid amount is confirmed to be 1.2 mmol / g by NH3-TPD).

[0020] A preferred embodiment of the preparation method of the zeolite catalyst for hydrogenating biomass oil to produce green aviation kerosene is that the noble metal salt solution is silver nitrate solution. The mass ratio of silver in the ZSM-5 zeolite and the silver nitrate solution is 100:(1-2).

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

[0022] A preferred embodiment of the preparation method of the zeolite catalyst for hydrogenating biomass oil to produce green aviation kerosene is that the solutes of the non-noble metal salt solution are tin sulfate and chromium nitrate. The mass ratio of tin, chromium in the ZSM-5 zeolite and the non-noble metal salt solution is 100:(6-10):(5-8).

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

[0024] In the third aspect, the present application proposes an application of a zeolite catalyst for hydrogenating biomass oil to produce green aviation kerosene, and adopts the following technical solution.

[0025] For an application of a zeolite catalyst for hydrogenating biomass oil to produce green aviation kerosene prepared by the above preparation method, add biomass oil and the zeolite catalyst into a reactor, heat to 200-210 °C, introduce hydrogen, and maintain the reaction at a pressure of 8-12 MPa for 1-3 h.

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

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

[0028] By adopting the above technical solution, biomass oil is fully hydrogenated. Among them, the hydrogen-oil volume ratio represents the volume of hydrogen gas in the standard state required for a unit volume of feedstock oil.

[0029] In summary, the zeolite catalyst for hydrogenating biomass oil to produce green aviation kerosene, its preparation method and application of the present application have the following beneficial effects: the cost of preparing the zeolite catalyst is relatively low, but when it is applied to catalyze the hydrogenation of biomass oil, the hydrogenation efficiency is high and the conversion rate is high. Detailed embodiments

[0030] The following is a clear and complete description of the implementation solutions of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the following embodiments, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present application.

[0031] Example 1 A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene includes the following steps.

[0032] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, and keep it at room temperature of 20 - 30 °C for 2 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 8 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 40 g / 1 L.

[0033] Organic phosphorus coupling: Add a small molecule organic phosphorus compound to the mixed solution, and react at 60 °C for 3 h to obtain a repaired solution. Among them, the small molecule organic phosphorus compound is trimethyl phosphate; the initial concentration of the added trimethyl phosphate is 100 g / L.

[0034] Metal loading: Filter the repaired solution to obtain the ZSM-5 molecular sieve repaired with organic phosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired with organic phosphorus, and calcine at 450 °C for 4 h to obtain the molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content in the silver nitrate solution is 1.5 g. The solute of the non-noble metal salt solution is tin sulfate and chromium nitrate. The tin content in the non-noble metal salt solution is 8 g, and the chromium content in the non-noble metal salt solution is 6 g.

[0035] The molecular sieve catalyst prepared in this example includes the following components: ZSM-5 molecular sieve repaired with organic phosphorus; noble metal component Ag, with a loading amount of 1.5 wt%; non-noble metal promoter Sn, with a loading amount of 8 wt%; non-noble metal promoter Cr, with a loading amount of 6 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material that has not been repaired with organic phosphorus.

[0036] Example 2 A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene includes the following steps.

[0037] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, and keep it at room temperature of 20 - 30 °C for 1 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 5 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 30 g / 1 L.

[0038] Organophosphorus coupling: Add a small-molecule organophosphorus compound to the mixed solution, react at 50 °C for 4 h to obtain a repair solution. Among them, the small-molecule organophosphorus compound is trimethyl phosphate; the initial concentration of trimethyl phosphate added is 80 g / L.

[0039] Metal loading: Filter the repair solution to obtain ZSM-5 molecular sieve repaired by organophosphorus. Drop the noble metal salt solution and non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organophosphorus, and calcine at 400 °C for 5 h to obtain a molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content in the silver nitrate solution is 1 g. The solutes of the non-noble metal salt solution are tin sulfate and chromium nitrate. The tin content in the non-noble metal salt solution is 6 g, and the chromium content in the non-noble metal salt solution is 5 g.

[0040] The molecular sieve catalyst prepared in this example includes the following components: ZSM-5 molecular sieve repaired by organophosphorus; noble metal component Ag, loading amount 1 wt%; non-noble metal promoter Sn, loading amount 6 wt%; non-noble metal promoter Cr, loading amount 5 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0041] Example 3 A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene includes the following steps.

[0042] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, keep it at room temperature of 20 - 30 °C for 3 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 10 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 50 g / 1 L.

[0043] Organophosphorus coupling: Add a small-molecule organophosphorus compound to the mixed solution, react at 70 °C for 2 h to obtain a repair solution. Among them, the small-molecule organophosphorus compound is trimethyl phosphate; the initial concentration of trimethyl phosphate added is 120 g / L.

[0044] Metal loading: Filter the repair solution to obtain ZSM-5 molecular sieve repaired by organophosphorus. Drop the noble metal salt solution and non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organophosphorus, and calcine at 500 °C for 3 h to obtain a molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content in the silver nitrate solution is 2 g. The solutes of the non-noble metal salt solution are tin sulfate and chromium nitrate. The tin content in the non-noble metal salt solution is 10 g, and the chromium content in the non-noble metal salt solution is 8 g.

[0045] The molecular sieve catalyst prepared in this example comprises the following components: organophosphorus-repaired ZSM-5 molecular sieve; noble metal component Ag with a loading amount of 2 wt%; non-noble metal promoter Sn with a loading amount of 10 wt%; non-noble metal promoter Cr with a loading amount of 8 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0046] Comparative Example 1 A molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene is prepared in this comparative example. The difference from Example 1 is that the solute of the non-noble metal salt solution only contains tin sulfate and does not contain chromium nitrate, as follows.

[0047] A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0048] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, keep it at room temperature of 20 - 30 °C for 2 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 8 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 40 g / 1 L.

[0049] Organophosphorus coupling: Add a small-molecule organophosphorus compound into the mixed solution, react at 60 °C for 3 h to obtain a repaired solution. Among them, the small-molecule organophosphorus compound is trimethyl phosphate; the initial concentration of trimethyl phosphate added is 100 g / L.

[0050] Metal loading: Filter the repaired solution to obtain the organophosphorus-repaired ZSM-5 molecular sieve, drop the noble metal salt solution and the non-noble metal salt solution into the organophosphorus-repaired ZSM-5 molecular sieve, and calcine at 450 °C for 4 h to obtain the molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content in the silver nitrate solution is 1.5 g. The solute of the non-noble metal salt solution is tin sulfate, and the tin content in the non-noble metal salt solution is 14 g.

[0051] The molecular sieve catalyst prepared in this example comprises the following components: organophosphorus-repaired ZSM-5 molecular sieve; noble metal component Ag with a loading amount of 1.5 wt%; non-noble metal promoter Sn with a loading amount of 14 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0052] Comparative Example 2 A molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene is prepared in this comparative example. The difference from Example 1 is that the solute of the non-noble metal salt solution only contains chromium nitrate and does not contain tin sulfate, as follows.

[0053] A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene comprises the following steps.

[0054] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, and keep it at room temperature of 20 - 30 °C for 2 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 8 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 40 g / 1 L.

[0055] Organophosphorus coupling: Add a small molecule organophosphorus compound to the mixed solution, and react at 60 °C for 3 h to obtain a repair solution. Among them, the small molecule organophosphorus compound is trimethyl phosphate; the initial concentration of trimethyl phosphate added is 100 g / L.

[0056] Metal loading: Filter the repair solution to obtain the ZSM-5 molecular sieve repaired with organophosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired with organophosphorus, and calcine at 450 °C for 4 h to obtain a molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content in the silver nitrate solution is 1.5 g. The solute of the non-noble metal salt solution is chromium nitrate, and the chromium content in the non-noble metal salt solution is 14 g.

[0057] The molecular sieve catalyst prepared in this example includes the following components: ZSM-5 molecular sieve repaired with organophosphorus; noble metal component Ag, with a loading amount of 1.5 wt%; non-noble metal promoter Cr, with a loading amount of 14 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired with organophosphorus.

[0058] Comparative Example 3 In this comparative example, a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene is prepared. The difference from Example 1 is that tetrabutylammonium fluoride is used instead of NH4F, and tetraethylphosphonium bromide is used instead of trimethyl phosphate, as follows.

[0059] A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene includes the following steps.

[0060] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the tetrabutylammonium fluoride solution, and keep it at room temperature of 20 - 30 °C for 2 h to obtain a mixed solution. Among them, the concentration of the tetrabutylammonium fluoride solution is 8 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the tetrabutylammonium fluoride solution is 40 g / 1 L.

[0061] Organophosphorus coupling: Add a small molecule organophosphorus compound to the mixed solution, and react at 60 °C for 3 h to obtain a repair solution. Among them, the small molecule organophosphorus compound is tetraethylphosphonium bromide; the initial concentration of tetraethylphosphonium bromide added is 100 g / L.

[0062] Metal loading: Filter the repair solution to obtain the ZSM-5 molecular sieve repaired by organophosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organophosphorus, and calcine at 450 °C for 4 h to obtain the molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content of the silver nitrate solution is 1.5 g. The solutes of the non-noble metal salt solution are tin sulfate and chromium nitrate. The tin content of the non-noble metal salt solution is 8 g, and the chromium content of the non-noble metal salt solution is 6 g.

[0063] The molecular sieve catalyst prepared in this example includes the following components: ZSM-5 molecular sieve repaired by organophosphorus; noble metal component Ag, loading amount 1.5 wt%; non-noble metal promoter Sn, loading amount 8 wt%; non-noble metal promoter Cr, loading amount 6 wt%. The above loading amounts are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0064] Comparative Example 4 In this comparative example, a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene was prepared. The difference from Example 1 is that the non-noble metal promoter Sn and the non-noble metal promoter Cr were replaced by Ni, specifically as follows.

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

[0066] Fluoride activation: Immerse 100 g of ZSM-5 molecular sieve into the NH4F solution, and keep it at room temperature of 20 - 30 °C for 2 h to obtain a mixed solution. Among them, the concentration of the NH4F solution is 8 g / L, and the mass ratio of the ZSM-5 molecular sieve to the volume of the NH4F solution is 40 g / 1 L.

[0067] Organophosphorus coupling: Add a small molecule organophosphorus compound to the mixed solution, and react at 60 °C for 3 h to obtain a repair solution. Among them, the small molecule organophosphorus compound is trimethyl phosphate; the initial concentration of trimethyl phosphate added is 100 g / L.

[0068] Metal loading: Filter the repair solution to obtain the ZSM-5 molecular sieve repaired by organophosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organophosphorus, and calcine at 450 °C for 4 h to obtain the molecular sieve catalyst. Among them, the noble metal salt solution is silver nitrate solution. The silver content of the silver nitrate solution is 1.5 g. The solute of the non-noble metal salt solution is nickel nitrate. The nickel content of the non-noble metal salt solution is 14 g.

[0069] The molecular sieve catalyst prepared in this example comprises the following components: organophosphorus-repaired ZSM-5 molecular sieve; noble metal component Ag with a loading of 1.5 wt%; non-noble metal promoter Ni with a loading of 14 wt%. The above loadings are the mass ratios of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

[0070] Application Example 1 Add 1 L of soybean oil and 0.5 g of the molecular sieve catalyst into the reactor, heat to 200 °C, introduce hydrogen, with a hydrogen flow rate of 50 mL / min and a hydrogen-to-oil volume ratio of 800:1, and maintain a reaction pressure of 10 MPa for 2 h. After the reaction, the conversion rate, isohydrocarbon ratio, carbon deposition rate, and 100-h activity retention rate are measured respectively, and the specific measurement methods are as follows.

[0071] 1) Determination of isohydrocarbon ratio (GC×GC-TOFMS) 1.1 Instruments: Comprehensive two-dimensional gas chromatography: Agilent 8890 + Zoex ZX2.

[0072] Mass spectrometry: Pegasus BT TOFMS.

[0073] 1.2 Analysis process: Select the hydrogenation product, and after performing deoxidation on a silica gel column, GC×GC separation, and TOFMS qualitative analysis in sequence, it is quantified by area normalization. The formula for the isohydrocarbon ratio is as follows: Isohydrocarbon ratio = peak area of isoparaffin / peak area of total hydrocarbons × 100%.

[0074] 2) Determination of carbon deposition rate (TGA) 2.1 Conditions: Instrument: Netzsch STA 449 F5.

[0075] Procedure: Take the post-reaction catalyst, heat it to 150 °C in an N2 atmosphere (to remove moisture) to obtain the dry weight m2, then switch to an air atmosphere, heat to 800 °C (to burn carbon), keep it at a constant temperature for 30 min, and then obtain the residual weight m3. The carbon deposition rate = (m2 - m3) / m2 × 100%.

[0076] 3) Determination of acid amount (NH3-TPD) 3.1 Parameters: Adsorption temperature: 100 °C.

[0077] Heating rate: 10 °C / min.

[0078] Detection: TCD signal.

[0079] Calculation of acid amount: Acid amount = A × K / m (mmol / g). Where A is the desorption peak area and K is the NH3 molar correction factor.

[0080] The molecular sieve catalysts prepared in Example 1 are characterized as shown in Table 1 below.

[0081]

[0082] The catalytic reaction data were tested according to the above method as shown in Table 2 below.

[0083]

[0084] In Table 2, the conversion rate and the proportion of isohydrocarbons are the data of the first catalytic reaction. The carbon deposition rate is the data of continuous catalysis for 100 h. The 100-h activity retention rate (%) is the result of dividing the conversion rate of soybean oil hydrogenation catalyzed by the molecular sieve catalyst after 100 h of continuous catalytic reaction by the conversion rate of the first catalytic hydrogenation of soybean oil.

[0085] In summary, the molecular sieve catalysts prepared in Examples 1-3 have a high conversion rate for catalytic hydrogenation of biomass oil. For example, the conversion rate of soybean oil catalyzed by the catalyst in Example 1 is 97% (confirmed by GC-MS that the proportion of C8-C16 hydrocarbons is 85%), the isohydrocarbons are 78% (the molecular sieve pore channels induce branching), and the ultra-low carbon deposition rate, and the carbon deposition rate after 100 h is only 0.3%.

[0086] The products of catalytic hydrogenation of biomass oil using the catalysts of the examples have excellent quality, meet the ASTM D7566 standard, and have great industrial value.

[0087] Although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene, characterized in that, It includes the following components: ZSM-5 molecular sieve repaired by organophosphorus; Noble metal component Ag, with a loading amount of 1-2 wt%; Non-noble metal promoter Sn, with a loading amount of 6-10 wt%; Non-noble metal promoter Cr, with a loading amount of 5-8 wt%; The said loading amount is the mass ratio of each element relative to the ZSM-5 molecular sieve raw material not repaired by organophosphorus.

2. A preparation method of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene as described in claim 1, characterized in that, It includes: Fluoride activation: Immerse the ZSM-5 molecular sieve into the NH4F solution and treat it at room temperature for 1-3 h to obtain a mixed solution; Organophosphorus coupling: Add a small molecule organophosphorus compound into the said mixed solution and react at 50-70 °C for 2-4 h to obtain a repaired solution; Metal loading: Filter the said repaired solution to obtain the ZSM-5 molecular sieve repaired by organophosphorus. Drop the noble metal salt solution and the non-noble metal salt solution into the ZSM-5 molecular sieve repaired by organophosphorus and calcine it at 400-500 °C for 3-5 h to obtain the molecular sieve catalyst.

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

4. The preparation method of the molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene according to claim 2, characterized in that, The said small molecule organophosphorus compound is trimethyl phosphate; the initial concentration of added trimethyl phosphate is 80-120 g / L.

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

6. The preparation method of the molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene according to claim 2, characterized in that, The solute of the said non-noble metal salt solution is tin sulfate and chromium nitrate; the mass ratio of the ZSM-5 molecular sieve to tin and chromium in the non-noble metal salt solution is 100:(6-10):(5-8).

7. Use of a molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene prepared by the preparation method according to any one of claims 2 to 6, characterized in that, Add biomass oil and the said molecular sieve catalyst into the reactor, heat it to 200-210 °C, introduce hydrogen, and maintain a reaction at a pressure of 8-12 MPa for 1-3 h.

8. Use of the molecular sieve catalyst for hydrogenating biomass oil to produce green aviation kerosene according to claim 7, characterized in that, The hydrogen-oil volume ratio is (700-900):1.

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