CN110918093A - Catalyst for hydrodeoxygenation reaction of biodiesel as well as preparation method and application of catalyst - Google Patents
Catalyst for hydrodeoxygenation reaction of biodiesel as well as preparation method and application of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for a hydrodeoxygenation reaction of biodiesel as well as a preparation method and application thereof. The catalyst is MnO-BaO-Al2O3The composite oxide is used as a carrier, metal Pt is used as an active component, and the auxiliary agent is Sn. The immersion method is adopted to prepare the supported catalyst with the active component Pt distributed on the carrier in an eggshell shape, and the auxiliary Sn is adopted to carry out the eggshell type Pt/MnO-BaO-Al2O3And modifying by using a composite catalyst. The catalyst has good effect on generating propylene by cracking biodiesel by matching with a radial reactor, and the prepared catalyst has high Pt utilization rate, good selectivity and high catalytic efficiency, and can fully utilize straight-chain carbon-containing radicalsThe high-quality biodiesel raw material is cracked to produce more propylene.
Description
Technical Field
The invention relates to a catalyst for a hydrodeoxygenation reaction of biodiesel as well as a preparation method and application thereof.
Background
Propylene is a common basic chemical raw material, is widely applied to the chemical fields of acrylonitrile, epoxy propylene, acetone and the like, and still has a larger gap in the market at present. The main chemical components of the biological oil and fat of animals, plants and the like are triglyceride formed by higher fatty acid and free higher fatty acid, mainly contain C, H, O element, and are green, environment-friendly and renewable energy sources. Meanwhile, due to the continuous progress of agricultural production technology, the yield of the biological grease is rapidly improved, and the production cost is also sharply reduced. In recent years, the great consumption of fossil energy and the decreasing reserves of fossil energy are increasingly reduced, and the conversion of renewable bio-oil into fossil crude oil resources becomes a research hotspot of practitioners.
US2007/0015947a1 discloses a process for the production of ethylene from renewable biological feedstocks. The method comprises the steps of pretreating raw materials by using biological grease containing triglyceride and free higher fatty acid as raw materials and acidic zeolite containing more than 0.7 nm of average pore diameter and less than or equal to 0.7 nm of average pore diameter as a catalyst, and then carrying out catalytic cracking in a riser reactor to obtain the C2-C5 olefin. According to the simulation results, when a soybean oil was used as a raw material, the reaction temperature was 565 ℃, the mass ratio of the catalyst to the raw material oil was 10, and the mass ratio of steam to the raw material was 0.1, the total yield of the C4 product having a boiling point of 50.8% or less in this method was obtained.
Oxygen mainly comprises micromolecular inorganic oxides CO and CO in the cracking process of the biodiesel2、H2Removing O in the form of fatty acid alkyl (R is fatty acid alkyl, R' is methyl or ethyl)) The distillate contains only a small amount of oxygen. Wherein about 70% of the oxygen content is removed mainly in the form of water. In order to improve the economy of the C, H atoms, hydrodeoxygenation should be carried out in a proper manner to reduce C, H atom loss.
The Pd, Pt and other noble metal hydrodeoxygenation catalysts not only have high activity, but also have strong anti-coking and anti-poisoning capabilities. Patent CN104437451 teaches that the catalyst has the problems of nonuniform platinum dispersion, low Pt utilization rate and low catalytic efficiency after roasting. The performance of a supported catalyst depends not only on the chemical composition of its supported component but also on the distribution of the supported component on the support. Because the supported components of the eggshell type catalyst are distributed on the outer surface of the carrier particles, Pt is easier to contact, the catalytic efficiency is higher, and the diffusion path is shorter; patent CN10594230 describes that the alumina after high temperature calcination still has the disadvantage of residual protonic acid center. The existence of the acid center can promote acid catalytic reactions such as polymerization, isomerization and the like, and influence the selectivity of the catalyst. In particular, when various polymers produced by the polymerization reaction adhere to the surface of the catalyst, the reactivity of the catalyst is lowered, and the catalyst is deactivated in a short time, which affects the life of the catalyst.
Therefore, a new hydrodeoxygenation catalyst is needed to improve the Pt catalytic efficiency and promote the preferential production of corresponding straight-chain hydrocarbons by biodiesel. Then the straight chain hydrocarbon is used as ideal paraffin-based raw material to crack and produce propylene, thereby reducing C, H atom loss and obtaining propylene with high selectivity.
Disclosure of Invention
Aiming at the defects of low Pt utilization rate and catalytic efficiency, residual carrier acid center, low selectivity and low economy of C, H atoms of the biodiesel of the hydrodeoxygenation catalyst, the catalyst for the biodiesel hydrodeoxygenation reaction and the preparation method thereof are provided.
The invention also provides application of the catalyst in producing propylene by catalytic cracking of biodiesel. The catalyst has a good effect on deep deoxygenation of the biodiesel, and has a good effect on cracking the biodiesel to generate propylene by matching with a radial reactor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for hydrodeoxygenation reaction of biodiesel adopts MnO-BaO-Al as a catalyst2O3The composite oxide is used as a carrier, metal Pt is used as an active component, and the auxiliary agent is Sn. Preferably, based on the mass of the catalyst, the content of Pt is 0.05-0.5 wt%, the content of auxiliary Sn is 0.05-1.0 wt%, the content of MnO is 1-5 wt%, the content of BaO is 10-20%, and the balance is Al2O3。
Preferably, the content of Sn is controlled to be 0.1-0.3 wt% based on the mass of the catalyst, and if the content of Sn is too much, the active site of metal Pt can be covered, and the activity is influenced; if too small, the modification effect on the active center Pt is weakened, and the influence on the catalyst performance is not obvious.
Preferably, the MnO content is controlled to be 2-3 wt% based on the mass of the catalyst, and if the MnO content is too high, the active sites of the metal Pt are covered, so that the activity is influenced; if the amount is too small, the acidity of the carrier surface is not reduced, and side reactions such as acid catalysis are difficult to suppress.
The supported catalyst with active component Pt distributed in an eggshell shape is prepared by adopting an immersion method, and Sn is adopted to carry out eggshell type Pt/MnO-BaO-Al2O3And (4) modifying the catalyst. The prepared catalyst Pt has high utilization rate and good selectivity.
The catalyst of the invention is prepared according to the following steps:
(1) heating soluble salt solution of aluminum, manganese and barium, neutralizing and controlling the pH value to be 9-10, then filtering, washing and acidifying until the pH value is 5-6 to obtain carrier slurry, dropwise adding the carrier slurry into an oil ammonia column, aging for 1-3h, drying and roasting to obtain the composite oxide pellet carrier. The concentration range of the soluble salt solution is 0.1-10mol/L, preferably 0.1-2 mol/L;
(2) soaking the composite oxide carrier obtained in the step (1) in a soluble platinum salt and soluble tin salt solution, drying and roasting to obtain a product catalyst, wherein the soaking time and the concentration of a soaking solution are changed to change the soaking amount of platinum and tin on the composite oxide carrier, and the concentration of the soluble platinum salt and the soluble tin salt solution ranges from 0.1mol/L to 10mol/L, and preferably ranges from 0.1mol/L to 2 mol/L.
According to the preparation method, the soluble salt solution of aluminum in the step (1) can be one or more of aluminum nitrate, aluminum trichloride and aluminum sulfate, and aluminum nitrate is preferred; the soluble salt solution of manganese may be manganese nitrate and/or manganese chloride, preferably manganese nitrate. The soluble salt solution of barium may be barium nitrate and/or barium chloride, preferably barium nitrate.
The preparation method of the catalyst comprises the steps of (2) respectively soaking the composite oxide carrier obtained in the step (1) in soluble platinum salt and soluble tin salt solutions or in a mixed solution of the soluble platinum salt and the soluble tin salt, drying and roasting to obtain the product catalyst. Namely, the introduction process of platinum and tin on the composite oxide carrier can be separately introduced step by step or introduced together.
In the preparation method of the catalyst, the solution in the step (1) is heated to 40-60 ℃; the drying temperature is 100-; the roasting temperature is 500-700 ℃, and the roasting time is 6-8 h.
In the preparation method of the catalyst, the dipping time in the step (2) is 2-12 h; the drying temperature is 100-; the roasting temperature is 500-600 ℃, and the roasting time is 6-8 h.
The catalyst of the invention can be used for producing propylene by catalytic cracking of biodiesel, and preferably, the biodiesel comprises at least one selected from triglyceride, diglyceride, monoglyceride, fatty acid methyl ester, fatty acid ethyl ester and free fatty acid, and the carbon chain of the fatty acid is a straight chain of C8-C22.
Preferably, the catalyst of the present invention is used in a method for cracking biodiesel, and the reaction conditions are as follows:
the reactor is a radial reactor which flows from top to bottom in a Z-shaped concentric manner, the upper part of the reactor is sequentially provided with a protective bed layer I and a hydrogenation bed layer II from inside to outside, and alkaline alumina and the hydrogenation and the dehydrogenation described in the patent are respectively filled in the protective bed layer I and the hydrogenation bed layer IIAn oxygen catalyst. The cracking bed layer III at the lower part of the reactor is filled with a ZSM-5 type molecular sieve catalyst and is used for the deep cracking of first-stage hydrocarbons. The reaction temperature of the protective bed and the hydrogenation bed is 30-270 ℃, preferably 30-100 ℃, the reaction pressure is 1-4MPa (gauge pressure), the molar ratio of hydrogen to biodiesel is 0.2-0.8: 1, liquid hourly space velocity of 2-20h-1. Realizing deep deoxidation of the biodiesel and preliminary cracking of fatty acid carbon chains. The conditions of the cracking bed III include: the reaction temperature is 400--1. The deep cracking of the hydrocarbon after the upper deoxidation is realized, and the yield of the propylene is increased. The hydrodeoxygenation catalyst needs to be subjected to reduction treatment before reaction, pure hydrogen is used for reduction, and the reduction condition is 450-550 ℃ and reduction lasts for 2-4 h.
The biodiesel is fed from the top of the radial reactor, sequentially passes through the protective bed layer I and the hydrogenation bed layer II, and a hydrocarbon product generated after passing through the hydrogenation bed layer II is contacted with a ZSM-5 type molecular sieve catalyst to generate propylene through cracking.
The technical scheme of the invention has the following advantages:
(1) the introduction of Mn and Ba in the synthesis process of the composite oxide carrier can effectively improve the stability of the catalyst, and reduce side reactions such as cracking and the like and the generation of carbon deposition in the hydrodeoxygenation process by reducing the acidity of the surface of the carrier.
(2) In the catalyst, the existence of Sn element can enhance the interaction between metal Pt and the carrier, improve the dispersion degree of the metal Pt and be beneficial to improving the stability of the Pt on the catalyst.
(3) According to the catalyst, the active component Pt is distributed on the carrier in an eggshell shape by controlling the dipping time and the dipping amount, and the active component is mainly distributed on the outer layer of the catalyst, so that Pt is easier to contact under the same number of active sites, and the catalytic efficiency is higher; the material is easy to contact with the active center; and the diffusion path is short, and the product is easy to remove from the active center, thereby being beneficial to improving the selectivity of the product. Namely, the catalyst has higher Pt metal utilization rate, and better catalyst activity and propylene selectivity in hydrogenation products.
(4) A radial reactor which flows from top to bottom and in a Z-shaped concentric manner is adopted, so that deep deoxygenation of a section of biodiesel and primary cracking of a fatty acid carbon chain (generation of a small amount of propylene) are well realized; the two-stage deoxygenation aliphatic hydrocarbon is deeply cracked to increase the yield of propylene.
(5) The catalyst can well solve the following defects in the catalytic cracking process of the biodiesel by combining with an adaptive radial reactor: 1. oxygen is CO, CO2、H2Form O, C, H high loss; 2. dehydrogenating linear hydrocarbon to form ring to produce arene product not easy to crack and convert into propylene; 3. the long straight carbon chain structure of the biodiesel is retained to the maximum extent, so that the biodiesel is used as an ideal paraffin-based raw material for producing propylene.
(6) The catalyst has high deoxidation activity under the low-temperature condition (30-100 ℃), and the conversion rate of oxygen-containing compounds can reach about 95%; combined with the adapted radial reactor, the selectivity of propylene based on carbon in the product is up to more than 45%, and the yield is more than 42% (about 18-22% of propylene yield in refinery residual oil cracking, about 25-30% of saturated biodiesel).
Description of the drawings: FIG. 1 is a schematic view of radial reactor catalyst packing.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
The gas product collection in the examples and comparative examples of the present invention was completed and tested by an Agilent 6890GC (TCD detector) online analytical compositional test method), and the test method of the present invention was selected from the group consisting of "analytical methods in petrochemical industry", edited by yang cui et al, scientific press, 1990.
Example 1
Catalyst preparation
(1) And (3) preparing a catalyst carrier. Weighing 60.294g Al (NO)3)3·9H2O (molecular weight: 375), 0.630g Mn (NO)3)2(molecular weight: 179) and 2.559g Ba (NO)3)2(molecular weight: 261) is dissolved in 150ml of deionized water to prepare a solution, and the solution is stirred for 1 hour; heating the solution to 60 ℃, neutralizing with 5 wt% sodium carbonate solution,controlling the pH value to be 9; filtering, washing with deionized water, acidifying with 10mol/L nitric acid solution until pH is 6, and stirring to sol state to obtain carrier slurry; dripping slurry into an oil ammonia column, shrinking sol into spherical gel, aging for 2h, taking out gel spheres, washing with deionized water, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 8h to obtain composite oxide carrier spheres;
(2) 0.057g of SnCl is weighed2·2H2O (molecular weight: 226) and 0.120g H2PtCl6·6H2Dissolving O (molecular weight: 518) in 250ml of hydrochloric acid solution with the concentration of 0.1mol/L to prepare solution, uniformly stirring, soaking the composite oxide carrier pellet obtained in the step (1) in the soaking solution for 2 hours, drying at 105 ℃ for 5 hours, and roasting at 550 ℃ for 6 hours to obtain a catalyst A;
the catalyst comprises the following components in percentage by mass: pt: 0.3 wt%, Sn: 0.2 wt%, MnO: 2.5 wt% and BaO 15.0 wt%.
Catalyst evaluation conditions: as shown in figure 1, the reactor adopts a radial reactor (Nicoti Ke Li chemical equipment Co., Ltd.), the reaction temperature of a protective bed layer I (filled with alkaline alumina, Shanghai Yangjiang chemical, 80-160 meshes) and a hydrogenation bed layer II (filled with a catalyst A) is 45 ℃, the reaction pressure is 4.0MPa, the molar ratio of hydrogen to methyl stearate (18:0) is 0.5, and the liquid hourly space velocity is 4h-1. Before the reaction, the hydrodeoxygenation catalyst needs to be reduced by pure hydrogen, the reduction temperature is 500 ℃, and the reduction time is 3 hours. The cracking bed layer III catalyst is selected from ZSM-5 type catalytic material (Shanghai New molecular sieves company, silica-alumina ratio 40-50, bulk density 0.72g/ml), the process conditions are 600 ℃, and the space velocity is 10h-1The reaction pressure was 4.0MPa, and the catalyst/gasoline ratio (mass ratio of catalyst to deoxygenated hydrocarbon product) was 8, and the catalytic effects are shown in Table 1.
Example 2
The catalyst preparation procedure was the same as in example 1.
Evaluation of catalyst: the evaluation conditions were the same as in example 1, and the evaluation raw material was changed to methyl oleate. The specific conditions are that the reactor adopts a radial reactor and a hydrogenation bed layer I (filled with alkaline alumina, Shanghai Yangjiang chemical, 80-1)60 meshes) and a hydrogenation bed layer II (filled with a catalyst A) at a reaction temperature of 45 ℃, a reaction pressure of 4.0MPa, a molar ratio of hydrogen to methyl oleate (18:1) of 0.5 and a liquid hourly space velocity of 4h-1. The catalyst needs to be reduced by pure hydrogen before reaction, the reduction temperature is 500 ℃, and the reduction time is 3 h. The cracking bed layer III catalyst is selected as ZSM-5 type catalytic material, the process conditions are 600 ℃, and the space velocity is 10h-1The reaction pressure was 4.0MPa, the catalyst-to-oil ratio was 8, and the catalytic effect was as shown in Table 1.
Example 3
(1) And (3) preparing a catalyst carrier. Weighing 57.904g Al (NO)3)39H2O (molecular weight: 375), 0.756g Mn (NO)3)2(molecular weight: 179) and 3.071g Ba (NO)3)2(molecular weight: 261) is dissolved in 150ml of deionized water to prepare a solution, and the solution is stirred for 1 hour; heating the solution to 45 ℃, neutralizing with 5 wt% sodium carbonate solution, and controlling the pH to 9; filtering, washing with deionized water, acidifying with 10mol/L nitric acid solution until pH is 6, and stirring to sol state to obtain carrier slurry; dropwise adding the slurry into an oil ammonia column, shrinking the sol into spherical gel, aging for 2h, taking out gel spheres, washing with deionized water, drying at 160 ℃ for 18h, and roasting at 550 ℃ for 8h to obtain composite oxide carrier spheres;
(2) weighing 0.028g SnCl2·2H2O (molecular weight: 226) and 0.060g H2PtCl6·6H2Dissolving O (molecular weight: 518) in 250ml of hydrochloric acid solution with the concentration of 0.1mol/L to prepare solution, uniformly stirring, soaking the composite oxide carrier pellet obtained in the step (1) in the soaking solution for 4 hours, drying at 120 ℃ for 7 hours, and roasting at 550 ℃ for 7 hours to obtain a catalyst B;
the catalyst comprises the following components in percentage by mass: pt: 0.15 wt%, Sn: 0.1 wt%, MnO: 3.0 wt% and BaO 18.0 wt%.
Catalyst evaluation conditions: the reactor adopts a radial reactor, the conditions of a protective bed layer I (filled with alkaline alumina, Shanghai Yangjiang chemical, 80-160 meshes) and a hydrogenation bed layer II (filled with a catalyst B) are that the reaction temperature is 55 ℃, the reaction pressure is 3.0MPa, and the molar ratio of hydrogen to methyl stearate (18:0) is 05, liquid hourly space velocity of 4h-1. And the catalyst B needs to be reduced by pure hydrogen before reaction, the reduction temperature is 550 ℃, and the reduction time is 3 h. The cracking bed layer III catalyst is selected as ZSM-5 type catalytic material, the process conditions are 550 ℃, and the space velocity is 10h-1The reaction pressure was 3.0MPa, the catalyst-to-oil ratio was 8, and the catalytic effect was as shown in Table 1.
Example 4
(1) And (3) preparing a catalyst carrier. Weighing 62.316g Al (NO)3)3·9H2O (molecular weight: 375), 0.504g Mn (NO)3)2(molecular weight: 179) and 2.048g Ba (NO)3)2(molecular weight: 261) is dissolved in 150ml of deionized water to prepare a solution, and the solution is stirred for 1 hour; heating the solution to 55 ℃, neutralizing with 5 wt% sodium carbonate solution, and controlling the pH to 9; filtering, washing with deionized water, acidifying with 10mol/L nitric acid solution until pH is 6, and stirring to sol state to obtain carrier slurry; dropwise adding the slurry into an oil ammonia column, shrinking the sol into spherical gel, aging for 2h, taking out gel spheres, washing with deionized water, drying at 140 ℃ for 17h, and roasting at 550 ℃ for 8h to obtain composite oxide carrier spheres;
(2) 0.228g of SnCl is weighed out2·2H2O (molecular weight: 226) and 0.179g H2PtCl6·6H2Dissolving O (molecular weight: 518) in 250ml of hydrochloric acid solution with the concentration of 0.1mol/L to prepare solution, uniformly stirring, soaking the composite oxide carrier pellet obtained in the step (1) in the soaking solution for 2 hours, drying at 160 ℃ for 5 hours, and roasting at 600 ℃ for 6 hours to obtain a catalyst C;
the catalyst comprises the following components in percentage by mass: pt: 0.45 wt%, Sn: 0.8 wt%, MnO: 2 wt% and BaO 12 wt%.
Catalyst evaluation conditions: the reactor adopts a radial reactor, the conditions of a protective bed layer I (filled with alkaline alumina, Shanghai Yangjiang chemical, 80-160 meshes) and a hydrogenation bed layer II (filled with a catalyst C) are 65 ℃, the reaction pressure is 2.5MPa, the molar ratio of hydrogen to methyl stearate (18:0) is 0.5, and the liquid hourly space velocity is 4h-1. The catalyst C needs to be reduced by pure hydrogen before reaction, the reduction temperature is 560 ℃,the reduction time was 4 h. The cracking bed layer III catalyst is selected as ZSM-5 type catalytic material, the process conditions are 580 ℃, and the space velocity is 10h-1The reaction pressure was 2.5MPa, the catalyst-to-oil ratio was 8, and the catalytic effect was as shown in Table 1.
Comparative example 1
The cracking feedstock was evaluated in the same manner as in example 1, using methyl stearate as a model compound for biodiesel. The reactor is a fixed bed reactor with the same specification. The catalyst filled in the reactor bed layer is ZSM-5 type catalytic material, the process conditions are 600 ℃, and the space velocity is 10h-1The reaction pressure was 4.0MPa, the catalyst-to-oil ratio was 8, and the catalytic effect was as shown in Table 1.
Comparative example 2
The cracking feedstock was evaluated in the same manner as in example 1, using methyl oleate as a model compound for biodiesel. The reactor is a fixed bed reactor with the same specification. The catalyst filled in the reactor bed layer is ZSM-5 type catalytic material, the process conditions are 600 ℃, and the space velocity is 10h-1The reaction pressure was 4.0MPa, the catalyst-to-oil ratio was 8, and the catalytic effect was as shown in Table 1.
TABLE 1 examples and comparative examples model the effect of compound oxygen conversion and propylene selectivity, yield
| Oxygen conversion% | Propylene selectivity/%) | Propylene yield/%) | |
| Example 1 | 99.89 | 49.70 | 48.21 |
| Example 2 | 97.67 | 48.54 | 45.63 |
| Example 3 | 95.43 | 45.99 | 42.31 |
| Example 4 | 99.93 | 51.60 | 49.54 |
| Comparative example 1 | 88.43 | 26.33 | 23.17 |
| Comparative example 2 | 87.62 | 25.24 | 21.45 |
The catalyst of the invention has high deoxidation activity under the condition of low temperature, and the conversion rate of oxygen-containing compounds can reach about 95 percent; by combining with an adaptive radial reactor, the selectivity of propylene based on carbon group in the product is up to more than 45%, and the yield is more than 42%.
Claims (10)
1. A catalyst for hydrodeoxygenation reaction of biodiesel, characterized in that the catalyst comprises a carrier MnO-BaO-Al2O3The composite oxide, active component metal Pt and auxiliary agent Sn.
2. The catalyst of claim 1 wherein the metal Pt is present in an amount of 0.05 to 0.5 wt%, the promoter Sn is present in an amount of 0.05 to 1.0 wt%, the MnO is present in an amount of 1 to 5 wt%, the BaO is present in an amount of 10 to 20%, and the balance is Al, based on the mass of the catalyst2O3。
3. The method for preparing the catalyst according to any one of claims 1 to 2, comprising the steps of:
(1) heating soluble salt solution of aluminum, manganese and barium, neutralizing and controlling the pH to be 9-10, then filtering, washing and acidifying until the pH is 5-6 to obtain carrier slurry, dropwise adding the carrier slurry into an oil ammonia column, aging for 1-3h, drying and roasting to obtain a composite oxide carrier;
(2) and (2) respectively soaking the composite oxide carrier obtained in the step (1) in soluble platinum salt and soluble tin salt solutions or in a mixed solution of the soluble platinum salt and the soluble tin salt, drying and roasting to obtain the product catalyst.
4. The method of claim 3, wherein the solution is heated to 40-60 ℃ in step (1); the drying temperature is 100-; the roasting temperature is 500-700 ℃, and the roasting time is 6-8 h.
5. The method according to claim 3, wherein the dipping time in the step (2) is 2 to 12 hours; the drying temperature is 100-; the roasting temperature is 500-600 ℃, and the roasting time is 6-8 h.
6. Use of the catalyst according to any one of claims 1 to 2 or the catalyst obtained by the method according to any one of claims 3 to 5 for the catalytic cracking of biodiesel to produce propylene, preferably, the biodiesel comprises at least one selected from the group consisting of triglycerides, diglycerides, monoglycerides, fatty acid methyl esters, fatty acid ethyl esters and free fatty acids, the carbon chain of which is a linear chain from C8 to C22.
7. The use according to claim 6, wherein the catalytic cracking reaction is carried out in a radial reactor, the radial reactor is a top-down Z-shaped concentric flow radial reactor, the upper part of the reactor is sequentially provided with a protective bed layer (I) and a hydrogenation bed layer (II) from inside to outside, and the protective bed layer and the hydrogenation bed layer are respectively filled with basic alumina, the catalyst according to any one of claims 1 to 2 or the catalyst prepared by the method according to any one of claims 3 to 5; the lower part of the reactor is a cracking bed layer (III) filled with a ZSM-5 type molecular sieve catalyst.
8. The use according to claim 7, characterized in that the protective bed (I) and the hydrogenation bed (II) are both reacted at a temperature of 30-100 ℃, at a pressure of 1-4MPa and at a molar ratio of hydrogen to biodiesel of 0.2-0.8: 1, liquid hourly space velocity of 2-20h-1。
9. The use according to claim 7, wherein the reaction conditions of the lower cracking bed (III) of the reactor comprise: the reaction temperature is 400-600 ℃, the product mass ratio of the ZSM-5 type molecular sieve catalyst to the hydrogenation bed layer (II) is 2-20, and the weight hourly space velocity is 2-30h-1。
10. The use as claimed in any one of claims 6 to 9, wherein the catalyst for the hydrodeoxygenation of biodiesel requires a reduction treatment before the reaction, wherein pure hydrogen is used for the reduction, and the reduction conditions are 450 ℃ and 550 ℃, and the reduction time is 2-4 h.
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