Sulfurized FeMo alloy catalyst as well as preparation and application thereof

Abstract

The invention discloses a sulfurized FeMo alloy catalyst as well as a preparation method and application thereof, and relates to the technical field of catalytic conversion of lignin. The preparation method of the catalyst comprises the following steps: calcining the carbon carrier in a tubular furnace to obtain biochar; biochar is soaked in a nitrogen-containing solution and then calcined, and modified activated carbon is obtained; putting a molybdenum source, an iron source and the modified activated carbon into a hydrothermal kettle, adding a sulfur source for hydrothermal reaction, and filtering and separating to obtain the catalyst. Transition metal Fe is introduced into the MoS2-based catalyst to promote electron transfer among species, then activation of H2 is promoted to generate a large amount of dissociation active hydrogen, the generated active hydrogen attacks C-O bonds in phenolic compounds, and high-selectivity cracking of the phenolic compounds is caused. Bimetals in the FeMo alloy catalyst interact with each other to form a metastable compound as an active component, so that the hydrocarbon monomer is obtained with high selectivity in the reaction.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic conversion of lignin, and particularly relates to a sulfided FeMo alloy catalyst, a preparation method thereof and an application thereof. Background Art

[0002] As the main component of lignocellulose, lignin is the only renewable aromatic compound raw material in nature. Developing and utilizing lignin depolymerization to produce green hydrocarbons helps to achieve the efficient utilization of biomass resources, thereby accelerating the realization of the goals of "carbon peak and carbon neutrality". The lignin macromolecule is mainly composed of three structural units disorderly connected and combined by C-C bonds and C-O bonds, and can be converted into bio-oil liquid fuel after depolymerization. However, the depolymerized lignin oil and its derivatives are mainly phenols, and their low H / C ratio and high oxygen content result in low energy density, so the products need to be further converted and upgraded. A widely used method for upgrading bio-oil is hydrodeoxygenation. There are mainly two paths for hydrodeoxygenation, namely hydrogenation first and then deoxygenation and direct deoxygenation. Among them, direct deoxygenation can retain the aromatic ring structure to prepare aromatic compounds and reduce hydrogen consumption.

[0003] Transition metal sulfides are inexpensive and easy to prepare. Among them, MoS2-based catalysts are an important type of heterogeneous catalyst in the hydrodeoxygenation process of lignin and its derivatives, especially having unique selectivity for aromatics. Currently, the main modification strategies for MoS2-based catalysts include stacking layer regulation, morphology control, defect site design, promoter metal doping, acid modification and support regulation, etc. The prior art has recorded the hydrodeoxygenation performance of non-supported NiMoS catalysts prepared by the hydrothermal method for p-cresol. The results show that the main role is the synergistic effect of MoS2 and NiS rather than the formation of the NiMoS active phase, and the consumption of raw materials for non-supported catalysts is large and the price cost is relatively high. Chinese Patent CN111233941B discloses a preparation method and application of an FeMoS catalyst for microwave-assisted catalytic depolymerization of lignin. This catalyst realizes the catalytic depolymerization of C-C bonds in lignin macromolecules, but the temperature is relatively high during the preparation and reaction processes, the energy consumption is greater, and it is difficult to break C-O bonds and hydrodeoxygenate phenolic compounds under high-power microwave assistance. As disclosed in Chinese Patent Application CN109174132A, a sulfide catalyst using CoAl hydrotalcite-like oxide as a support and loading MoS2 as an active component by a hydration method is disclosed. The active component of this catalyst is evenly dispersed and has relatively high catalytic activity, but the complete conversion of reactants and the complete deoxygenation of phenolic compounds have not been achieved yet. In addition, the selection of CoAl hydrotalcite-like oxide as the support results in relatively high raw material costs.

[0004] The formation of alloys in the catalyst can promote better dispersion of the metal phase on the surface of the support, and the synergistic effect between the bimetals can effectively promote electron transfer. It can be known from the relevant literature reports of the prior art that due to the presence of the Ni-Fe alloy, the bimetallic Ni-Fe catalyst exhibits higher activity than the monometallic Ni in the hydrodeoxygenation process of phenol, which is attributed to the increased adsorption strength of the Ni-Fe alloy for the intermediate cyclohexanol. The presence of Ni-Fe alloy particles is conducive to the formation of more oxygen vacancies as deoxygenation active centers. There is a strong interaction between the oxygenophilic metal Fe and the hydroxyl oxygen. Therefore, it is of great significance to develop a sulfided FeMo alloy catalyst to achieve high activity and high deoxygenation rate in the hydrodeoxygenation reaction of lignin alcoholysis bio-oil. Summary of the Invention

[0005] The present invention provides a sulfided FeMo alloy catalyst, which comprises a support and an active component supported on the support; the support is a modified activated carbon;

[0006] The active component comprises Mo and Fe, the total loading amount of the active component is 20%, and the metal molar ratio Fe / (Fe + Mo) is 0.25.

[0007] In addition, the present invention also provides a method for preparing the above-mentioned sulfided FeMo alloy catalyst, which specifically comprises the following steps:

[0008] S1. Placing the carbon support in a tubular furnace and calcining it in a nitrogen atmosphere to obtain biochar;

[0009] S2. Preparing a nitrogen-containing solution from a nitrogen source and carrying out a hydrothermal reaction with the biochar in a hydrothermal device;

[0010] S3. Calcining the impregnated support in a nitrogen atmosphere to obtain modified activated carbon;

[0011] S4. Preparing a solution from a molybdenum source and an iron source, placing the activated carbon obtained in S3 in the solution and stirring evenly, placing it in a hydrothermal autoclave and adding a sulfur source for hydrothermal reaction, filtering and separating after the reaction, and drying to obtain an activated carbon-supported sulfided FeMo alloy catalyst.

[0012] Preferably, the carbon support described in step S1 is selected from one of wood charcoal, fruit shell charcoal, coconut shell charcoal or petroleum coke charcoal;

[0013] The calcination temperature is 400 - 600 °C, the calcination time is 2 - 3 h, and the heating rate is 2 - 5 °C / min. Preferably, the calcination temperature is 600 °C. At this temperature, the specific surface area and pore volume of the obtained biochar are relatively high, and the high specific surface area is conducive to the uniform dispersion of the metal active component.

[0014] Preferably, the nitrogen source described in step S2 is one or more of melamine, urea, aniline;

[0015] The mass-volume ratio of the carrier to the nitrogen-containing solution is 1:1 to 1:3;

[0016] The mass fraction of the nitrogen source in the nitrogen-containing solution is 1-20 wt%, preferably, the mass fraction of the nitrogen-containing solution is 10 wt%. At this concentration, nitrogen doping can not only effectively improve the electronic structure and electron delocalization on the carrier carbon, introduce more oxygen adsorption sites, but also will not damage the original carrier pores;

[0017] The thermal reaction temperature is 70 °C and the time is 2-12 h.

[0018] Preferably, the calcination in step S3 is carried out at a heating rate of 2-5 °C / min at 700-900 °C for 1-3 h.

[0019] Preferably, the molybdenum source in step S4 is one of ammonium paramolybdate, ammonium tetrathiomolybdate and molybdenum acetylacetonate.

[0020] Preferably, the transition metal salt in step S4 is one of ferric nitrate, ferric sulfate and ferrous sulfate.

[0021] Preferably, the sulfur source in step S4 is one of thiourea, dimethyl disulfide and carbon disulfide.

[0022] Preferably, the hydrothermal reaction in step S4 includes: reacting at 120-180 °C for 12-24 h; the drying condition is vacuum drying at 60 °C for 8 h.

[0023] The present invention also proposes an application of the sulfided FeMo alloy catalyst in the hydrodeoxygenation reaction of lignin phenolic derivatives. In specific applications, lignin phenolic derivatives are used as raw materials, n-hexane is selected as the solvent, and hydrocarbon compounds are produced by reacting in a magnetic stirring autoclave under the reaction conditions of 280-360 °C and an initial hydrogen pressure of 1-4 MPa.

[0024] The structural formula of the above lignin phenolic derivatives is as follows:

[0025]

[0026] In the formula, OR1 is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy or 2-propoxy, and R2 is H, 4-methyl, 4-ethyl, 3-methoxy, 4-methoxy, 5-methoxy or 6-methoxy.

[0027] In the hydrodeoxygenation reaction, the phenolic hydroxyl group and methoxy or ethoxy or propoxy in the lignin phenolic derivative molecule are reduced.

[0028] Further, the lignin phenolic derivative in the present invention is selected as 4-ethylguaiacol, and the structural formula is as follows:

[0029]

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] (1) In the specific implementation process of the present invention, the biochar pyrolysis carbonization process is simple and easy to operate. The nitrogen source selected for nitrogen doping modification is inexpensive, and the cost of the loaded Fe and Mo transition metal salts is also not high. These advantages make the preparation method of this catalyst extremely economical and can effectively control the cost input.

[0032] (2) The activated carbon supported sulfided FeMo alloy catalyst obtained by the preparation process has highly dispersed metal particles on its surface. This characteristic endows the catalyst with excellent hydrogenation activity and makes it perform outstandingly in related reactions.

[0033] (3) The present invention successfully prepares the FeMo alloy through a series of precise operations. Due to the stronger electronegativity of the Mo species inside the alloy, the electrons of the Fe species transfer to Mo. This electron transfer process effectively promotes the activation of H2, and then a large amount of dissociated active hydrogen is generated. These active hydrogens can accurately attack the C-O bond in the reactant, promoting the formation of deoxygenated hydrocarbon monomers and providing a key basis for subsequent reactions.

[0034] (4) The sulfided FeMo alloy catalyst in the present invention can achieve a conversion rate and deoxygenation rate of >99.9% for 4-ethylguaiacol, and shows good universality for other lignin phenolic derivatives during the substrate expansion process. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0036] Figure 1 are the X-ray diffraction patterns of the catalysts FeMoS / NC, MoS / NC, and FeS / NC prepared in Example 1, Comparative Example 1, and Comparative Example 2;

[0037] Figure 2 are the X-ray photoelectron spectroscopy diagrams of the catalysts FeMoS / NC, MoS / NC, and FeS / NC prepared in Example 1, Comparative Example 1, and Comparative Example 2;

[0038] Figure 3 are the transmission electron microscopy diagrams of the catalysts FeMoS / NC, MoS / NC, and FeS / NC prepared in Example 1, Comparative Example 1, and Comparative Example 2;

[0039] Figure 4 It is the GC-MS diagrams before and after the lignin alcoholysis bio-oil reaction in Experimental Example 7. Specific Embodiments

[0040] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that, without conflict, the following embodiments and the features in the embodiments may be combined with each other; and, based on the embodiments in the present disclosure, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present disclosure.

[0041] The following describes various aspects of embodiments within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present disclosure, those skilled in the art should understand that one aspect described herein may be implemented independently of any other aspect, and two or more of these aspects may be combined in various ways. For example, any number of aspects described herein may be used to implement an apparatus and / or practice a method. Additionally, this apparatus and / or this method may be implemented using other structures and / or functionality in addition to one or more of the aspects described herein.

[0042] Unless otherwise specified, the materials in the embodiments are prepared according to existing methods or directly purchased from the market.

[0043] Example 1

[0044] Preparation of biochar (C): Place 6 g of dry coconut shell in a tubular furnace, and then heat it to 500 °C at a flow rate of 40 mL / min and a heating rate of 2 °C / min in a nitrogen atmosphere for 3 h, and then cool it to room temperature;

[0045] Preparation of activated carbon (NC): First, prepare a 20 mL melamine solution with a mass fraction of 10 wt%, add 2 g of activated carbon, and continuously stir overnight at 70 °C. After taking it out, centrifuge and vacuum dry it at 105 °C for 12 h. After drying, calcine it at 700 °C in a tubular furnace under N2 atmosphere for 3 h;

[0046] Preparation of FeMoS / NC catalyst: First, add 30 mL of deionized water to prepare a solution containing 0.081 g of ferrous sulfate heptahydrate and 0.154 g of ammonium paramolybdate, and stir to dissolve. Put the obtained solution together with 0.5 g of the above-prepared NC and 0.3 g of thiourea into a 50 mL hydrothermal autoclave, react at 180 °C for 24 h, after cooling to room temperature, wash it several times with deionized water, and dry it in a vacuum oven at 60 °C for 12 h to obtain FeMoS / NC.

[0047] Comparative Example 1

[0048] Preparation of biochar (C): Place 6 g of dry coconut shells in a tubular furnace, and then heat them to 500 °C at a flow rate of 40 mL / min and a heating rate of 2 °C / min under a nitrogen atmosphere for 3 h, and then cool them to room temperature;

[0049] Preparation of activated carbon (NC): First, prepare 20 mL of a melamine solution with a mass fraction of 10 wt%, add 2 g of activated carbon, and continuously stir overnight at 70 °C. After taking it out, centrifuge and vacuum dry at 105 °C for 12 h. After drying, calcine in a tubular furnace under a N2 atmosphere at 700 °C for 3 h;

[0050] Preparation of MoS / NC catalyst: First, add 30 mL of deionized water to prepare a solution containing 0.154 g of ammonium heptamolybdate, and stir to dissolve. Put the obtained solution together with 0.5 g of the above-prepared NC and 0.3 g of thiourea into a 50 mL hydrothermal autoclave, react at 180 °C for 24 h, cool to room temperature, wash several times with deionized water, and dry in a vacuum oven at 60 °C for 12 h to obtain MoS / NC.

[0051] Comparative Example 2

[0052] Preparation of biochar (C): Place 6 g of dry coconut shells in a tubular furnace, and then heat them to 500 °C at a flow rate of 40 mL / min and a heating rate of 2 °C / min under a nitrogen atmosphere for 3 h, and then cool them to room temperature;

[0053] Preparation of activated carbon (NC): First, prepare 20 mL of a melamine solution with a mass fraction of 10 wt%, add 2 g of activated carbon, and continuously stir overnight at 70 °C. After taking it out, centrifuge and vacuum dry at 105 °C for 12 h. After drying, calcine in a tubular furnace under a N2 atmosphere at 700 °C for 3 h;

[0054] Preparation of FeS / NC catalyst: First, add 30 mL of deionized water to prepare a solution containing 0.081 g of ferrous sulfate heptahydrate, and stir to dissolve. Put the obtained solution together with 0.5 g of the above-prepared NC and 0.3 g of thiourea into a 50 mL hydrothermal autoclave, react at 180 °C for 24 h, cool to room temperature, wash several times with deionized water, and dry in a vacuum oven at 60 °C for 12 h to obtain FeS / NC.

[0055] The present invention also respectively tests and analyzes the above three catalysts, among which, Figure 1It is the X-ray diffraction pattern of Example 1 and Comparative Examples 1-2. In the figure, the characteristic diffraction peaks of the FeS2 crystal phase (PDF#37-0475) are at 2θ = 25.8o, 33.2o, 37.2o, 38.9o, and 52.0o. Only weak characteristic peaks of MoS2 are observed at 2θ = 32.2o and 57.4o, and no obvious diffraction peaks are observed at other positions. This may be due to the uniform dispersion of the MoS2 phase on the surface of the carrier. In the catalyst FeS / NC, the diffraction peaks at 2θ = 25.8o and 33.2o have relatively large intensities, sharp and symmetric profiles, corresponding to the characteristic diffraction peaks of the (110) and (101) crystal planes respectively. Compared with the single metal, in the bimetallic catalyst FeMoS / NC, the characteristic peaks at 25.8o and 33.2o shift to higher angles. This is because metal Mo enters the FeS2 lattice, effectively adjusting the size of the MoS2 lattice fringes, and Fe and Mo form an alloy.

[0056] Figure 2 It is the transmission electron microscopy image of the catalyst, where Figure 2 a, d, Figure 2 b, e and Figure 2 c, f correspond to the catalysts of Example 1, Comparative Example 1, and Comparative Example 2 respectively. Obvious agglomeration phenomena appear in the single-metal catalyst, while the metal particles in the bimetallic catalyst are evenly dispersed, indicating that the incorporation of Fe improves the dispersion of MoS2 on the surface of NC and is conducive to enhancing the interaction between metals. In Figure 2 d, two kinds of lattice fringes with different spacings can be observed. Compared with Comparative Example 2, the lattice spacing of the (002) plane of MoS2 in Example 1 decreases from 0.673 nm to 0.601 nm. This may be because small-radius Fe atoms (117Pm) are doped into the lattice of Mo atoms (130Pm), resulting in a decrease in the lattice spacing.

[0057] Figure 3 It is the X-ray photoelectron spectroscopy diagram of Example 1 and Comparative Examples 1-2. In Example 1, the characteristic peak of Mo shifts to higher binding energy, and the characteristic peak of Fe shifts to lower binding energy. The transfer of electrons from Fe to Mo reduces the electron cloud density of Mo, indicating a strong interaction between Fe and Mo.

[0058] In addition, for the specific application of the catalyst in the hydrodeoxygenation of lignin phenolic derivatives, a sulfided FeMo alloy catalyst was used as the catalyst, n-hexane was used as the solvent, and 4-ethylguaiacol was used as the raw material. The reaction was carried out in a magnetic stirring autoclave under the reaction conditions of 280 - 360 °C and an initial hydrogen pressure of 1 - 4 MPa for 1 - 6 h. Then, it was cooled to room temperature, the reaction mixture was taken out, and the filtrate and solid mixture were obtained by centrifugal separation. Finally, the conversion rate, deoxygenation rate of 4-ethylguaiacol, and selectivity of aromatics of the sulfided FeMo alloy catalyst were analyzed. The specific calculation formulas for the above three are as follows:

[0059] The calculation formula for the conversion rate is: Conversion rate of 4-ethylguaiacol (%) = (Molar amount of 4-ethylguaiacol in the raw material - Molar amount of unreacted 4-ethylguaiacol) ÷ Molar amount of 4-ethylguaiacol in the raw material × 100%.

[0060] The calculation formula for the deoxygenation rate is: Deoxygenation rate of 4-ethylguaiacol (%) = Molar amount of hydrocarbons generated / Molar amount of 4-ethylguaiacol consumed × 100%.

[0061] The calculation formula for the selectivity is: Selectivity of the product (%) = (Molar amount of the product / (Molar amount of the reactant in the raw material - Molar amount of the unreacted reactant)) × 100%.

[0062] The specific experimental procedure is as follows:

[0063] Experimental Example 1

[0064] 40 g of n-hexane was added to a 100 mL autoclave. 0.2 g of 4-ethylguaiacol and 0.1 g of the catalyst were injected into the reactor. After the reaction kettle was sealed, hydrogen was passed through for leak detection, and the air in the reaction kettle was replaced with hydrogen 3 times. Then, 3 MPa of hydrogen was charged into the reactor. The system was heated to 340 °C at a heating rate of 10 °C / min, and the stirring speed was adjusted to 700 r / min. The reaction was carried out under these conditions for 300 min. After the reaction was completed, the reactor was cooled to room temperature in the air. The product was qualitatively analyzed using an Agilent gas chromatograph-mass spectrometer, and the product was quantitatively analyzed using a gas chromatograph.

[0065] Table 2 Analysis results of the reaction products

[0066]

[0067] The hydrodeoxygenation activity of the catalyst was compared by analyzing the conversion rate of 4-ethylguaiacol and the hydrocarbon yield after hydrogenation. The specific results are shown in Table 2. By comparing FeMoS / NC with MoS / NC, it can be seen that the addition of Fe increases the selectivity of ethylbenzene. The Fe species acts as an oxygenophilic active site to adsorb oxygen-containing compounds and forms strong bonds with oxygen-containing functional groups. At the same time, the presence of Fe causes some vacancies due to sulfur loss to promote hydrogen activation, increasing the active sites. While promoting the hydrogenation of the C-O group, it inhibits the hydrogenation of the aromatic ring. Compared with the catalysts loaded with single metals, FeMoS / NC has the highest deoxygenation rate and aromatic hydrocarbon yield, proving the high hydrodeoxygenation activity of this catalyst. This may be because the formation of the alloy has a higher dispersion and the catalyst has a larger specific surface area, exposing more reactive sites. In addition, the formation of the FeMo alloy leads to a greater degree of electron transfer, and the synergistic effect between the two metals results in better catalytic activity.

[0068] Experimental Example 2

[0069] Except that the reaction time was 3 h, the reactant was phenol, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The conversion rate of phenol was 100%, among which the selectivity of benzene was 95.9% and the selectivity of cyclohexane was 4.1%.

[0070] Experimental Example 3

[0071] Except that the reaction time was 3 h, the reactant was p-cresol, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The conversion rate of p-cresol was 100%, among which the selectivity of toluene was 88.9% and the selectivity of methylcyclohexane was 11.1%.

[0072] Experimental Example 4

[0073] Except that the reaction time was 5 h, the reactant was guaiacol, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The conversion rate of guaiacol was 100%, among which the selectivity of toluene was 13.5%, the selectivity of benzene was 63.7%, and the selectivity of cyclohexane was 17.3%.

[0074] Experimental Example 5

[0075] Except that the reaction time was 8 h, the reactant was eugenol, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The conversion rate of eugenol was 100%, among which the selectivity of n-propylbenzene was 73.1%, the selectivity of 3-methylpropylbenzene was 5.2%, the selectivity of 4-methylpropylbenzene was 16.9%, and the selectivity of propylcyclohexane was 15.8%.

[0076] Experimental Example 6

[0077] Except that the reaction time was 8 h, the reactant was 2,6-dimethoxyphenol, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The conversion rate of 2,6-dimethoxyphenol was 100%, among which the selectivity of benzene was 50.9%, the selectivity of toluene was 34.8%, and the selectivity of methylcyclohexane was 14.3%.

[0078] Experimental Example 7

[0079] Except that the reaction time was 12 h, the reactant was the bio-oil obtained by lignin alcoholysis, and the catalyst was obtained in Example 1, other reaction conditions and test methods were the same as those in Experimental Example 1. The total ion chromatograms of the reactant and the product are as Figure 4 shown. The deoxygenation rate was 99%, the selectivity of aromatic hydrocarbons was 66.5%, and the selectivity of cycloalkanes was 33.0%, indicating that the catalyst had good hydrodeoxygenation activity in the real system.

[0080] As described above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A sulfided FeMo alloy catalyst, the catalyst comprising a carrier and an active component supported on the carrier; characterized in that, The carrier is modified activated carbon; The active components include Mo and Fe, the total loading amount of the active components is 20%, and the metal molar ratio Fe / (Fe + Mo) is 0.

25.

2. A method for preparing the sulfided FeMo alloy catalyst as claimed in claim 1, characterized in that, It includes the following steps: S1. Place the carbon carrier in a tubular furnace and calcine it in a nitrogen atmosphere to obtain biochar; S2. Prepare a nitrogen-containing solution from the nitrogen source and conduct a thermal reaction with the biochar in a hydrothermal device; S3. Calcinate the impregnated carrier in a nitrogen atmosphere to obtain modified activated carbon; S4. Prepare a solution from the molybdenum source and the iron source, place the activated carbon obtained in S3 into the solution and stir evenly, place it in a hydrothermal autoclave, add a sulfur source and conduct a hydrothermal reaction, filter and separate after the reaction, and dry to obtain a sulfurized FeMo alloy catalyst supported on activated carbon.

3. The preparation method according to claim 2, characterized in that, The carbon carrier described in step S1 is selected from one of wood charcoal, fruit shell charcoal, coconut shell charcoal or petroleum coke charcoal; The calcination temperature is 400 - 600 °C, the calcination time is 2 - 3 h, and the heating rate is 2 - 5 °C / min.

4. The preparation method according to claim 2, wherein, The nitrogen source described in step S2 is one or more of melamine, urea, aniline; The mass-volume ratio of the carrier to the nitrogen-containing solution is 1:1 - 1:3; The mass fraction of the nitrogen source in the nitrogen-containing solution is 1 - 20 wt%; The thermal reaction temperature is 70 °C and the time is 2 - 12 h.

5. The preparation method according to claim 2, wherein The calcination in step S3 is carried out at a heating rate of 2 - 5 °C / min at 700 - 900 °C for 1 - 3 h.

6. The preparation method according to claim 2, wherein, The molybdenum source in step S4 is one of ammonium paramolybdate, ammonium tetrathiomolybdate and molybdenum acetylacetonate.

7. The preparation method according to claim 6, characterized in that, The iron source in step S4 is one of iron nitrate, iron sulfate, ferrous sulfate.

8. The preparation method according to claim 7, characterized in that, The sulfur source in step S4 is one of thiourea, dimethyl disulfide, carbon disulfide.

9. The preparation method according to any one of claims 6-8, characterized in that, The hydrothermal reaction in step S4 includes: reacting at 120 - 180 °C for 12 - 24 h; the drying condition is vacuum drying at 60 °C for 8 h.

10. Use of a sulfided FeMo alloy catalyst prepared by the method according to claim 1 or any one of claims 2-9 in the catalytic hydrodeoxygenation reaction of lignin phenolic derivatives, characterized in that, Using lignin phenolic derivatives as raw materials, selecting n-hexane as the solvent, reacting in a magnetic stirring autoclave under the reaction conditions of 280 - 360 °C and an initial hydrogen pressure of 1 - 4 MPa to produce hydrocarbon compounds.

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