A supported transition metal phosphide catalyst, its preparation method and use

Abstract

The application discloses a supported transition metal phosphide catalyst and a preparation method and application thereof. The supported transition metal phosphide catalyst comprises the following components: (1) a carrier; and (2) an active component, which is a transition metal phosphide; wherein the nanoparticle particle size of the transition metal phosphide is 5-30 nm. The catalyst provided by the application has the characteristics of high activity and long service life when used in a pyrolysis gasoline hydrodesulfurization reaction.

Description

Technical Field

[0001] This invention relates to the field of catalytic technology for hydrodesulfurization of cracked gasoline, and in particular to a supported transition metal phosphide catalyst, its preparation method, and its application. Background Technology

[0002] Cracked gasoline, primarily composed of C5-C9 hydrocarbons, is a key byproduct of naphtha cracking to ethylene production. Due to its high aromatic content, it is often used as a feedstock for downstream aromatics extraction. However, because the sulfur compounds in it are toxic to aromatics extraction catalysts, cracked gasoline requires hydrodesulfurization (HDS) treatment. Therefore, research on the HDS catalytic process and related technologies for cracked gasoline is extremely important for improving aromatics extraction efficiency.

[0003] The hydrodesulfurization (HDS) process in cracked gasoline involves the conversion of sulfur-containing compounds (such as thiophene, thiols, and thioethers) into H2S under the action of a catalyst. In recent years, researchers have discovered that transition metal phosphide catalysts exhibit high hydrodesulfurization activity. Under the same test conditions, the Ni2P / SiO2 catalyst shows higher HDS activity for dibenzothiophene than both NiMo / Al2O3 and CoMo / Al2O3, and the activity order for similar phosphides is: Ni2P > WP > MoP > CoP > Fe2P [Journal of Catalysis, 2003, 216, 343-352]. Furthermore, due to the high mechanical strength and thermal stability of transition metal phosphides, they show great promise as a substitute for commercial sulfide catalysts.

[0004] Previous literature reports that the HDS process of transition metal phosphides is a structure-sensitive reaction. Taking the Ni2P / SiO2 catalyst system as an example, Oyama et al. [Journal of Catalysis, 2008, 258, 393-400] found that as the Ni2P grain size decreases, the number of pyramidal coordinated Ni(2) sites increases, while the number of tetrahedral coordinated Ni(1) sites remains unchanged. The surface Ni / P ratio decreases, the activity increases, the selectivity of direct desulfurization (DDS) decreases, and the selectivity of hydrogen desulfurization (HYD) increases. There are few reports and studies on developing synthetic methods for Ni2P active component catalysts with different particle sizes to improve the activity and stability of the HDS reaction. Summary of the Invention

[0005] The technical problem to be solved by the present invention is the low activity of cracked gasoline in hydrodesulfurization in the prior art. The present invention provides a supported transition metal phosphide catalyst, its preparation method and application. The catalyst is used in the hydrodesulfurization reaction of cracked gasoline and has the characteristics of high activity and long service life. Moreover, the preparation cost is low and the process is relatively simple and controllable.

[0006] The first aspect of this invention provides a supported transition metal phosphide catalyst, comprising:

[0007] (1) Carrier;

[0008] (2) The active component is a transition metal phosphide;

[0009] Among them, the nanoparticles of transition metal phosphides have a particle size of 5–30 nm.

[0010] Furthermore, the nanoparticles of the transition metal phosphide have a particle size of 6.5–14.2 nm.

[0011] Furthermore, the support accounts for 80% to 99% of the catalyst weight.

[0012] Furthermore, the active component, transition metal phosphide, accounts for 1% to 20% of the catalyst weight.

[0013] Furthermore, the catalyst is free of nitrogen, bromine, and arsenic impurities, with a content of less than 5 ppm.

[0014] Further, the transition metal in the transition metal phosphide is selected from at least one element from Group VIB or Group VIII, wherein the Group VIB element is selected from Mo and / or W, and the Group VIII element is selected from at least one element from Fe, Co, and Ni. Preferably, the transition metal is at least one element from Co and Ni.

[0015] Furthermore, the support is selected from at least one oxide or molecular sieve support selected from Al2O3, SiO2 and TiO2, preferably a molecular sieve support, and more preferably MCM-41.

[0016] A second aspect of this invention provides a method for preparing the above-mentioned supported transition metal phosphide catalyst, comprising the following steps:

[0017] (1) Dissolve fatty acid metal salts and fatty acids in an organic solvent and heat under an inert atmosphere to obtain a mixed solution containing metal oxides;

[0018] (2) Take the mixed solution containing metal oxides obtained in step (1) and mix it with the carrier, stir and evaporate to dryness, then dry and calcine to obtain solid I; then take the acid-base regulator and mix it with water, add the obtained solid I, stir, dry and calcine to obtain solid II;

[0019] (3) The solid II obtained in step (2) is mixed with phosphate, heat-treated under a reducing atmosphere, and then surface passivated to obtain the supported transition metal phosphide catalyst.

[0020] Further, in step (1), the fatty acid metal salt is preferably an oleic acid metal salt, and the fatty acid is selected from fatty acids with 14 to 20 carbon atoms, preferably oleic acid.

[0021] Further, in step (1), the mass ratio of the fatty acid metal salt to the fatty acid is (10-45):1.

[0022] Further, in step (1), the mass ratio of the fatty acid to the organic solvent is (0.04 to 0.08):1.

[0023] Further, in step (1), the solvent is at least one of tetradecene, hexadecene, or octadecene.

[0024] Further, in step (1), the inert atmosphere is selected from at least one of nitrogen, argon, or helium. The inert atmosphere treatment process involves applying the inert atmosphere for 2-3 hours. -1 Degas at volume hourly space velocity for 30–60 min.

[0025] Further, in step (1), the heating is programmed heating, specifically heating at a rate of 2 to 10 °C / min to 260 to 360 °C, holding for 20 to 90 min, and then cooling to room temperature.

[0026] Further, in step (1), after heating, the straight-chain alkane solvent is used for washing and separation, wherein the straight-chain alkane has 6 to 10 carbon atoms, preferably n-hexane.

[0027] Further, in step (1), the specific separation process of separating with straight-chain alkanes is as follows: precipitation is performed with anhydrous ethanol (water content less than 0.5%), followed by centrifugation; the separated product is dispersed in straight-chain alkanes, precipitated again with ethanol, followed by centrifugation; this step is repeated 3 to 5 times; the obtained precipitate is added with straight-chain alkanes to obtain a hexane solution in which the metal oxide is uniformly dispersed, wherein the metal content is 1 to 5 mg / mL.

[0028] Further, in step (1), the preparation process of the fatty acid metal salt is as follows:

[0029] Anhydrous ethanol, water, and n-hexane are mixed to obtain a mixed solvent; transition metal chloride salts and fatty acid salts are added to the mixed solvent to obtain a mixed solution; the solution is then heated and separated to obtain the fatty acid metal salt.

[0030] Further, the volume ratio of anhydrous ethanol, water and n-hexane is (10-30):(10-30):(30-50); the molar ratio of transition metal chloride salt hydrate and fatty acid salt is (0.3-0.5):1.

[0031] Further, the transition metal chloride salt is selected from at least one of NiCl2·6H2O, CoCl2·6H2O, FeCl3·6H2O, and (NH4)2MoO4; the fatty acid in the fatty acid salt is selected from fatty acids with 14 to 20 carbon atoms, preferably sodium oleate.

[0032] Furthermore, the heat treatment is carried out at 60–70°C for 3–5 hours.

[0033] Furthermore, the separation is performed by washing with deionized water and separating the supernatant using a separatory funnel; the above steps are repeated several times; excess solvent is removed by vacuum distillation to obtain fatty acid metal salts.

[0034] Furthermore, in step (2), the ratio of the mixed solution containing metal oxides to the carrier is (10-100) mL: 1 g.

[0035] Further, in step (2), the support is selected from at least one oxide or molecular sieve support among Al2O3, SiO2 and TiO2, preferably a molecular sieve support, and more preferably MCM-41.

[0036] Further, in step (2), the stirring is carried out at 10-40°C for 8-24 hours; the drying conditions are vacuum drying at 100-120°C for 8-12 hours; and the calcination conditions are calcination at 300-500°C for 2-6 hours.

[0037] Further, in step (2), the mass ratio of the acid-base regulator, solid I, and deionized water is (0.05-1): 1:20.

[0038] Further, in step (2), the acid-base regulator is selected from NH4F and / or boric acid.

[0039] Further, in step (3), the molar ratio of metal in solid II obtained in step (2) to phosphorus in phosphate is (0.3-3):1.

[0040] Further, in step (3), the inert atmosphere is selected from at least one of nitrogen, argon, or helium. The inert atmosphere treatment process involves applying the inert atmosphere for 2-3 hours. -1 Degas at volume hourly space velocity for 30–60 min.

[0041] Furthermore, in step (3), the heat treatment is carried out in a reducing atmosphere for 2-3 hours. -1The temperature is increased to 350-500°C at a volume hourly space velocity of 2-10°C / min and held for 1-3 hours; the reducing atmosphere is selected from at least one of H2, H2 / Ar mixture, H2 / N2 mixture, and H2 / He mixture, preferably H2.

[0042] Further, in step (3), the surface passivation treatment is performed in a 0.5-1 vol.% O2 / N2 mixed gas for 2-3 hours.

[0043] The third aspect of this invention provides the application of the above-mentioned supported transition metal phosphide catalyst in the hydrodesulfurization reaction of cracked gasoline.

[0044] Furthermore, the catalyst needs to undergo a pre-sulfurization process before it can undergo the hydrodesulfurization reaction of cracked gasoline. The pre-sulfurization process and reaction conditions are as follows: sulfides are prepared with solvent to achieve a sulfur content of 400–3000 ppm in the sulfurized oil; hydrogen is introduced at a pressure of 2.6–3.0 MPa, with a hydrogen to catalyst volume ratio of (10–100):1; the catalyst bed is heated to 160–180°C, and sulfurized oil is introduced at a sulfurized oil space velocity of 3.0–5.0 h⁻¹. -1 Continue heating the catalyst bed to 280-320℃ at a rate of 20-40℃ / h, maintain the temperature for 20-40 hours, then allow it to cool naturally to 220-230℃, stop feeding the sulfiding oil, and the sulfidation process is complete.

[0045] Furthermore, the reaction conditions are as follows: reaction temperature of 250–350°C, reaction pressure of 2.5–3.5 MPa, and volume hourly space velocity of 0.5–2.0 h⁻¹. -1 .

[0046] Compared with the prior art, the present invention has the following advantages:

[0047] 1. The catalyst provided by this invention contains transition metal phosphide nanoparticles with a specific particle size of 5-30 nm. It is used in the hydrodesulfurization reaction of cracked gasoline and has the characteristics of high activity and long service life.

[0048] 2. The catalyst preparation method provided by the present invention utilizes the controllable synthesis of transition metal oxides followed by phosphating. The resulting transition metal phosphides are not only low in preparation cost, but also relatively simple, controllable, and free of impurities.

[0049] 3. The catalyst provided by this invention exhibits outstanding catalytic performance in the hydrodesulfurization reaction of cracked gasoline, including high conversion rate and long service life. Attached Figure Description

[0050] Figure 1(1) is the XRD pattern of the catalyst of Comparative Example 1; (2) is the XRD pattern of the catalyst of Comparative Example 2; (3) is the XRD pattern of the catalyst of Example 5.

[0051] Figure 2 Here is an HRTEM image of the catalyst in Example 5;

[0052] Figure 3 HRTEM image of the catalyst in Comparative Example 1. Detailed Implementation

[0053] The present invention will now be described in detail with reference to specific embodiments. These embodiments are for illustrative purposes only and do not constitute any limitation thereof. The invention has been described with reference to exemplary embodiments, but it should be understood that the terms used are descriptive and explanatory, not limiting. Modifications and revisions can be made to the invention within the scope of the claims as specified herein, without departing from the scope and spirit of the invention. Although the invention described herein relates to specific methods, materials, and embodiments, it does not imply that the invention is limited to the specific examples disclosed herein; on the contrary, the invention can be extended to all other methods and applications with the same function.

[0054] In the context of this specification, X-ray diffraction (XRD) analysis of the catalyst was performed on a Rigaku D / max-2200PC X-ray diffractometer, using Cu Kα radiation, tube voltage 40 kV, tube current 30 mA, scan rate 10° / min, and scan range 10°–80°.

[0055] In the context of this specification, the microstructure, particle size, and phase composition of the catalyst were observed using high-resolution transmission electron microscopy (HRTEM). A Tecnai G2 F20 HRTEM system was used for analysis. This system is equipped with a field emission gun with an accelerating voltage of 200 kV. High-resolution images were captured and acquired using a Gatan Ultrascan 2k×2k CCD camera with a point resolution of up to 0.2 nm. The sample preparation process was as follows: the sample powder was ground uniformly in an agate mortar, and then a small amount of powder was dispersed in anhydrous ethanol and ultrasonically dispersed. Two to three drops of the clear liquid were then added to a carbon-coated copper grid using a dropper. The average particle size was measured using Nano Measurer software, selecting more than 300 nanoparticles from a random field of view.

[0056] In the context of this specification, the content of active components and impurities in the catalyst is obtained by ICP analysis, wherein the ICP analysis is performed on a Vista-MPX inductively coupled plasma atomic emission spectrometer from Varian Corporation, USA.

[0057]

Example 1

[0058] Measure 25 mL of anhydrous ethanol, 20 mL of deionized water, and 36 mL of n-hexane and prepare a mixed solvent; weigh 7.0 g of NiCl2·6H2O and 40.0 g of sodium oleate and dissolve them evenly in the above mixed solvent; heat the above mixture to 60 °C and maintain for 3 h, then wash with 1000 mL of deionized water and separate using a separatory funnel, and take the supernatant; repeat the above steps 3 times; remove excess solvent by vacuum distillation to obtain nickel oleate, denoted as A1;

[0059] Take 10g Al, 1g oleic acid and 18.0g tetradecene, and dissolve them completely; then, under N2 atmosphere, allow the solution to dissolve for 2.5 hours. -1 The gas was degassed at volume hourly space velocity (VHSV) for 30 min; the temperature was increased to the thermal decomposition temperature of 260 °C at a rate of 5 °C / min and held for 30 min, then cooled to room temperature; precipitation was carried out with 200 mL of anhydrous ethanol (water content less than 0.5%), centrifuged at 9000 r / min, and the separated product was dispersed in 100 mL of n-hexane, and then precipitated with 100 mL of anhydrous ethanol. This step was repeated 3 times; the resulting precipitate was finally transferred to a volumetric flask, and 500 mL of n-hexane was added to make up to the final volume, resulting in a uniformly dispersed NiO solution in n-hexane, denoted as B1;

[0060] Take 50 mL of the above B1 solution and mix it with 5.0 g of MCM-41 carrier; stir at room temperature for 12 h, evaporate to dryness using a rotary evaporator; vacuum dry at 120 °C for 12 h, calcine under air purging conditions at 300 °C for 2 h, and cool naturally to obtain a solid powder, denoted as C1;

[0061] Weigh 0.1 g of NH4F, dissolve it in deionized water, stir well, and add it to Cl. The mass ratio of NH4F, Cl, and deionized water is 0.1:1:20. Stir at room temperature for 8 hours, vacuum dry at 120°C for 8 hours, and then dry in air for 2.5 hours. -1 The solid powder was obtained by purge with volume hourly space velocity, calcined at 300°C for 3 hours, and naturally cooled, and denoted as D1.

[0062] D1 powder was mixed evenly with 1.0 g of sodium hypophosphite monohydrate, wherein the molar ratio of metal in D1 to phosphorus in phosphate was 1:3. The mixture was then heated in a tube furnace under a N2 atmosphere for 2.5 h. -1 Degassing was performed at a volume hourly space velocity (VHSV) for 30 minutes, followed by degassing at a volume hourly space velocity (VHSV) for 2.5 hours under an H2 atmosphere. -1 The volume hourly space velocity was increased to 350℃ at a rate of 5℃ / min and held for 2h; after natural cooling, a 0.5-1 vol.% O2 / N2 mixed gas was introduced for surface passivation for 2.5h, and finally catalyst SS1 was obtained.

[0063] The transition metal phosphide nanoparticles of catalyst SS1 have a particle size of 6.5–8.2 nm. The active component, transition metal phosphide, accounts for 9.8% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0064]

Example 2

[0065] The catalyst preparation method is the same as in [Example 1], except that the thermal decomposition temperature is changed from 260℃ to 300℃; the final catalyst is SS2; the nanoparticle size of the transition metal phosphide in catalyst SS2 is 7.1-9.6 nm. The active component, transition metal phosphide, accounts for 10.1% of the catalyst weight. The catalyst does not contain nitrogen, bromine, or arsenic impurities.

[0066]

Example 3

[0067] The catalyst preparation method is the same as in [Example 1], except that the thermal decomposition temperature is changed from 260℃ to 340℃; the final catalyst is SS3; the nanoparticle size of the transition metal phosphide in catalyst SS3 is 7.5–10.9 nm. The active component, transition metal phosphide, accounts for 9.6% of the catalyst weight. The catalyst does not contain nitrogen, bromine, or arsenic impurities.

[0068]

Example 4

[0069] The catalyst was prepared using the same method as in Example 1, except that the 18.0g tetradecene was replaced with 20.0g hexadecene, and the thermal decomposition temperature was changed from 260℃ to 300℃; the final catalyst was SS4.

[0070] The transition metal phosphide nanoparticles of catalyst SS4 have a particle size of 8.0–11.6 nm. The active component, transition metal phosphide, accounts for 10.5% of the catalyst by weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0071]

Example 5

[0072] The catalyst preparation method is the same as in [Example 1], except that the 18.0g tetradecene is replaced with 22.5g octadecene, and the thermal decomposition temperature is changed from 260℃ to 320℃; the final catalyst is SS5.

[0073] The transition metal phosphide nanoparticles of catalyst SS5 have a particle size of 7.8–10.2 nm. The active component, transition metal phosphide, accounts for 10.4% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0074]

Example 6

[0075] The catalyst preparation method is the same as in [Example 1], except that the support is changed from MCM-41 to SiO2 support; the final catalyst obtained is SS6.

[0076] The nanoparticles of the transition metal phosphide catalyst SS6 have a particle size of 6.9–12.2 nm. The active component, transition metal phosphide, accounts for 11.0% of the catalyst by weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0077]

Example 7

[0078] The catalyst preparation method is the same as in [Example 1], except that the support is changed from MCM-41 to TiO2 support; the final catalyst obtained is SS7.

[0079] The transition metal phosphide nanoparticles of catalyst SS7 have a particle size of 8.2–13.5 nm. The active component, transition metal phosphide, accounts for 10.8% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0080]

Example 8

[0081] The catalyst was prepared using the same method as in [Example 1], except that 0.1g of NH4F was replaced with 0.12g of boric acid; the final catalyst was SS8.

[0082] The nanoparticles of the transition metal phosphide catalyst SS8 have a particle size of 10.9–14.2 nm. The active component, transition metal phosphide, accounts for 9.5% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0083]

Example 9

[0084] The catalyst preparation method is the same as in [Example 1], except that 1.0 g of sodium hypophosphite monohydrate is changed to 1.5 g of sodium hypophosphite, and the reduction temperature is changed from 350 °C to 450 °C; the final catalyst SS9 is obtained.

[0085] The nanoparticles of the transition metal phosphide catalyst SS9 have a particle size of 7.9–13.8 nm. The active component, transition metal phosphide, accounts for 11.5% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0086]

Example 10

[0087] The catalyst preparation method is the same as in [Example 1], except that 7.0g NiCl2·6H2O is replaced with 10.6g CoCl2·6H2O; the final catalyst is SS10.

[0088] The nanoparticles of the transition metal phosphide catalyst SS10 have a particle size of 7.7–12.2 nm. The active component, transition metal phosphide, accounts for 10.2% of the catalyst's weight. The catalyst is free of nitrogen, bromine, and arsenic impurities.

[0089]

Comparative Example 1

[0090] Weigh 7.8 g of Ni(NO3)2·6H2O and 7.2 g of (NH4)2HPO4, dissolve them in 30 mL of distilled water, add 1.0 mL of dilute nitric acid until the solution is clear, then add 10 g of support, stir for 8 h, let stand for 8 h of aging, dry overnight at 120 °C, and calcine at 5 °C / min to 500 °C for 3 h. Then transfer to a tube furnace for programmed temperature reduction of the catalyst precursor: in a hydrogen flow of 100 mL / min, increase to 600 °C at 2 °C / min and hold for 2 h. After natural cooling to room temperature, passivate the surface by introducing 0.5–1 vol.% O2 / N2 mixed gas for 2.5 h. Catalyst BJ1 is obtained.

[0091] [Comparative Example 2]

[0092] At room temperature, 6.9 g of nickel acetylacetonate (Ni(acac)2), 14.1 g of triphenylphosphine (PPh3), and 10.0 g of support were added to 40 mL of trioctylamine (TOA). Under nitrogen protection, the mixture was reacted at 320 °C for 3 h with stirring throughout the reaction. After the reaction was complete, the solution was cooled to 60 °C under nitrogen protection and then filtered. A 1:1 volume ratio ethanol-carbon tetrachloride solution was prepared, and the solution was washed, filtered, and dried at room temperature to obtain the catalyst precursor BJ2. The reduction process was then repeated as in Comparative Example 1 to obtain catalyst BJ2.

[0093]

Example 11

[0094] Before the catalysts of Examples 1-10 and Comparative Examples 1-2 undergo the HDS process, a pre-sulfurization process is required. The process and reaction conditions are as follows: sulfides are prepared with solvent to achieve a sulfur content of 3000 ppm in the sulfurized oil; hydrogen is introduced at a pressure of 3.0 MPa, with a hydrogen-to-catalyst volume ratio of 50:1; the catalyst bed is heated to 160°C, and sulfurized oil is introduced at a sulfurized oil space velocity of 4.0 h⁻¹. -1 Continue heating the catalyst bed to 320°C at a rate of 30°C / h, maintain the temperature for 40 hours, then allow it to cool naturally to 220°C, stop feeding the sulfiding oil, and the sulfidation process is complete.

[0095] A fixed-bed reactor was charged with 5.0 g of catalyst, with an inlet temperature of 240 °C, a pressure of 2.5 MPa, a hydrogen / oil volume ratio of 600:1, and a fresh oil space velocity of 2.0 h⁻¹. -1 Under the reaction conditions, a two-stage hydrogenation reaction was carried out on a simulated cracked gasoline component (a mixed solution of 3000 ppm thiophene and decahydronaphthalene). The desulfurization rate and stability during the reaction were analyzed. The results are shown in Table 1.

[0096] Table 1 Catalytic performance of the examples and comparative examples

[0097] catalyst Active components Desulfurization rate / % Desulfurization rate stabilized above 95% for a period of time per hour SS1 <![CDATA[Ni2P]]> 96.7 100 SS2 <![CDATA[Ni2P]]> 97.4 100 SS3 <![CDATA[Ni2P]]> 98.8 110 SS4 <![CDATA[Ni2P]]> 99.4 115 SS5 <![CDATA[Ni2P]]> 99.7 150 SS6 <![CDATA[Ni2P]]> 95.3 80 SS7 <![CDATA[Ni2P]]> 96.6 80 SS8 <![CDATA[Ni2P]]> 96.4 90 SS9 <![CDATA[Ni2P]]> 99.8 120 SS10 CoP 95.6 50 BJ1 <![CDATA[Ni2P]]> 91.0 — BJ2 <![CDATA[Ni2P]]> 93.5 —

[0098] Note: "—" indicates that it is not applicable.

Claims

1. A supported transition metal phosphide catalyst, comprising: (1) a support; (2) an active component being a transition metal phosphide, wherein the transition metal is selected from at least one of Group VIB or Group VIII elements; wherein the nanoparticle size of the transition metal phosphide is 5-30 nm; a preparation method of the supported transition metal phosphide catalyst, comprising the following steps: (1) dissolving a fatty acid metal salt and a fatty acid in an organic solvent, heating under an inert atmosphere to obtain a mixed solution containing metal oxides; (2) mixing the mixed solution containing metal oxides obtained in step (1) with a support, stirring and evaporating to dryness, then drying and calcining to obtain solid I; mixing an acid-base adjusting agent with water, adding the obtained solid I, stirring, drying, and calcining to obtain solid II; (3) mixing the solid II obtained in step (2) with a phosphate salt, heat treating under a reducing atmosphere, and then performing surface passivation treatment to obtain the supported transition metal phosphide catalyst.

2. The catalyst according to claim 1, characterized in that, The support accounts for 80-99% of the weight of the catalyst, and the active component transition metal phosphide accounts for 1-20% of the weight of the catalyst.

3. The catalyst of claim 1, wherein The content of nitrogen, bromine, and arsenic impurities in the catalyst is less than 5 ppm.

4. The catalyst of claim 1, wherein The Group VIB element is selected from Mo or / and W, and the Group VIII element is selected from at least one of Fe, Co, and Ni.

5. The catalyst of claim 4, wherein The transition metal is at least one of Co and Ni.

6. The catalyst of claim 1, wherein The support is at least one oxide selected from Al2O3, SiO2, and TiO2, or a molecular sieve support.

7. The catalyst of claim 6, wherein The support is a molecular sieve support.

8. The catalyst of claim 7, wherein The support is MCM-41. 9.A preparation method of the supported transition metal phosphide catalyst according to any one of claims 1-8, comprising the following steps: (1) dissolving a fatty acid metal salt and a fatty acid in an organic solvent, heating under an inert atmosphere to obtain a mixed solution containing metal oxides; (2) mixing the mixed solution containing metal oxides obtained in step (1) with a support, stirring and evaporating to dryness, then drying and calcining to obtain solid I; mixing an acid-base adjusting agent with water, adding the obtained solid I, stirring, drying, and calcining to obtain solid II; (3) mixing the solid II obtained in step (2) with a phosphate salt, heat treating under a reducing atmosphere, and then performing surface passivation treatment to obtain the supported transition metal phosphide catalyst.

10. The method of claim 9, wherein, In step (1), the fatty acid metal salt is a metal salt of oleic acid, and the fatty acid is selected from fatty acids with carbon number of 14-20.

11. The preparation method according to claim 9, characterized in that, In step (1), the fatty acid is selected from oleic acid.

12. The method of claim 9, wherein, In step (1), the mass ratio of the fatty acid metal salt to the fatty acid is (10-45): 1, and the mass ratio of the fatty acid to the organic solvent is (0.04-0.08):

1.

13. The preparation method according to claim 9, characterized in that, The organic solvent is at least one of tetradecene, hexadecene, or octadecene.

14. The method of claim 9, wherein, In step (1), the heating is programmed temperature heating, specifically heating at a rate of 2-10 ℃ / min to 260-360 ℃, maintaining for 20-90 min, and then cooling to room temperature.

15. The preparation method according to claim 9, characterized in that, In step (2), the ratio of the mixed solution containing metal oxides to the support is (10-100) mL: 1 g.

16. The method of claim 9, wherein, In step (2), the mass ratio of the acid-base regulator, the solid I and deionized water is (0.05-1):1:20; in step (3), the molar ratio of the metal in the solid II obtained in step (2) to the phosphorus in the phosphate is (0.3-3):

1.

17. The preparation method according to claim 9, characterized in that, In step (3), the heat treatment is carried out in a reducing atmosphere for 2-3 hours. -1 The volumetric space velocity is increased to 350-500℃ at a rate of 2-10℃ / min and held for 1-3h; the reducing atmosphere is selected from at least one of H2, H2 / Ar mixture, H2 / N2 mixture, and H2 / He mixture.

18. The method of claim 9, wherein, In step (3), the reducing atmosphere is selected from H2.

19. Use of the supported transition metal phosphide catalyst as claimed in any one of claims 1-8 for hydrodesulfurization of pyrolysis gasoline.

20. The use according to claim 19, characterized in that, The reaction conditions of the reaction are as follows: the reaction temperature is 250-350℃, the reaction pressure is 2.5-3.5MPa, the volume space velocity is 0.5-2.0h -1 .

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