Catalyst for capturing silicon and phosphorus through hydrogenation as well as preparation and application of catalyst

Abstract

The invention provides a catalyst for capturing silicon and phosphorus through hydrogenation and preparation and application thereof, and relates to the technical field of catalysts, the catalyst is mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier; in the catalyst, the nickel oxide accounts for 1 wt%-6 wt%, the molybdenum trioxide accounts for 4 wt%-9 wt%, and the silicon dioxide accounts for 0.1 wt%-0.7 wt%; the carrier contains aluminum oxide, carbon and ferrous oxide; the proportion of ferrous oxide in the catalyst is 0.2 wt%-3wt%. The catalyst provided by the invention has double functions of capturing silicon and phosphorus, can be used in a distillate oil hydrogenation device as a catalyst for capturing silicon and phosphorus in high-activity distillate oil hydrogenation, solves the problem that the removal of silicon and phosphorus in distillate oil mainly depends on a single capturing catalyst in the prior art, and has a wide application prospect. The technical effect of simultaneously removing silicon and phosphorus impurities in the distillate oil raw material is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, in particular to a hydrogenation silicon-phosphorus capturing catalyst and its preparation and application. Background Art

[0002] During crude oil extraction, silicone additives are often added to increase crude oil recovery. These additives readily decompose into small-molecule cyclosiloxane compounds during crude oil refining, entering the gasoline and diesel fractions. Furthermore, defoamers are typically added to suppress foaming within the coke drum during the delayed coking process in refineries. Silicon-containing defoamers are the most widely used. Silicon-containing defoamers primarily consist of polysiloxanes, which readily decompose at high temperatures into small-molecule cyclosiloxanes that enter the coking products, particularly the gasoline and diesel fractions.

[0003] As crude oil becomes increasingly inferior, the proportion of high-sulfur and high-acid crude oil processed in refineries continues to increase, resulting in increasingly serious corrosion problems in atmospheric and vacuum distillation units. Production personnel generally use corrosion inhibitors to reduce the corrosion rate of equipment and pipelines. Phosphorus-based corrosion inhibitors are widely used, mainly phosphate corrosion inhibitors. Due to fluctuations in crude oil properties, the amount of corrosion inhibitor added is not accurately controlled, which often leads to excessive phosphate esters remaining in the atmospheric and vacuum distillates and entering the subsequent distillate oil processing units.

[0004] Silicon and phosphorus in distillate oil are easily deposited into the catalyst pore structure during the catalyst hydroprocessing process, blocking the pores, reducing the specific surface area and pore volume of the catalyst, reducing the catalyst activity, causing permanent poisoning and deactivation of the catalyst, and seriously affecting the smooth operation of the device.

[0005] Prior art CN02129043.1 proposes a method for removing organic silicon compounds from distillate oil by adsorption separation. The adsorbent is composed of aluminum oxide and silicon oxide, and can be desorbed and regenerated using an alcohol-containing alkaline solution to achieve continuous and stable desiliconization operation. However, it can be seen from the examples that the silicon adsorption capacity of the adsorbent is relatively low, and the maximum amount of silicon adsorbed per kilogram of adsorbent does not exceed 20 grams; Prior art CN200910188090.0 discloses a coking naphtha silicon scavenger and its application method, which is prepared using aluminum oxide as a carrier, silicon dioxide as an auxiliary agent, and W, Mo, and Ni as hydrogenation components. Silicon dioxide is added during the preparation of the carrier. The silicon scavenger is mainly used to remove impurity silicon from coking naphtha and protect the coking naphtha hydrogenation silicon scavenger from silicon poisoning; Prior art CN201310397681 discloses a method for preparing a desiliconizer suitable for deep desiliconization of coking distillate oil, which uses aluminum oxide and MCM-41 molecular sieve as carriers, Ni and W as active components, The addition of molecular sieves increases the production cost of silicon scavengers to a certain extent; the prior art CN201410173293 discloses a desiliconizer, a preparation method thereof, and an application thereof, wherein the desiliconizer contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier is pseudo-boehmite and a mesoporous Y-type molecular sieve. During the preparation of the desiliconizer, the mesoporous Y-type molecular sieve needs to be synthesized first, and the molecular sieve synthesis process is relatively lengthy; the prior art CN115247080A discloses a coking gasoline and diesel desiliconization process and a desiliconizer preparation method, wherein the desiliconizer preparation method first obtains a mixed slurry through a gelation reaction, and then ages, filters, washes, dries, and shapes the slurry to obtain a desiliconization catalyst; the prior art CN93117674.3 discloses a scavenger for removing arsenic and / or phosphorus from petroleum materials, and a preparation method thereof, wherein the scavenger is prepared by impregnating nickel oxide and a small amount of platinum oxide and / or palladium oxide on a carrier through exchange or precipitation, and the scavenger needs to be reduced first during use.

[0006] In summary, the existing technology for removing silicon and phosphorus from distillate oil mainly uses a single capture catalyst. Some refineries' existing distillate oil raw materials contain both silicon and phosphorus impurities. Considering the physical and chemical properties of silicon and phosphorus impurities in distillate oil, it is very necessary to design and develop a catalyst with dual silicon and phosphorus capture functions.

[0007] In view of this, the present invention is proposed. Summary of the Invention

[0008] One of the purposes of the present invention is to provide a hydrogenation silicon-phosphorus capture catalyst having the dual functions of capturing silicon and phosphorus and capable of simultaneously removing silicon and phosphorus impurities from distillate oil feedstock.

[0009] The second object of the present invention is to provide a method for preparing a catalyst for hydrogenation to capture silicon and phosphorus, which has a simple process, is easy to operate, has a high success rate, and can form a core-shell structure in the catalyst, which is beneficial to improving the adsorption and capture and fixation effect of silicon and phosphorus impurities.

[0010] The third object of the present invention is to provide an application of a hydrogenation silicon and phosphorus capture catalyst, which can effectively remove silicon and phosphorus impurities in distillate oil raw materials, thereby protecting the main catalyst from poisoning and deactivation.

[0011] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0012] In the first aspect, a catalyst for hydrogenating silicon and phosphorus is mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0013] The nickel oxide in the catalyst accounts for 1 wt% to 6 wt%, the molybdenum trioxide accounts for 4 wt% to 9 wt%, and the silicon dioxide accounts for 0.1 wt% to 0.7 wt%;

[0014] The carrier contains aluminum oxide, carbon and ferrous oxide;

[0015] The ferrous oxide accounts for 0.2 wt% to 3 wt% in the catalyst.

[0016] Furthermore, the nickel oxide content in the catalyst is 2 wt% to 5 wt%;

[0017] Preferably, the molybdenum trioxide content in the catalyst is 5 wt% to 9 wt%;

[0018] Preferably, the content of silicon dioxide in the catalyst is 0.2 wt% to 0.5 wt%.

[0019] Furthermore, the ferrous oxide accounts for 0.5 wt% to 2 wt% in the catalyst.

[0020] Furthermore, the proportion of alumina in the carrier is 83wt% to 92wt%, and the proportion of carbon is 2wt% to 4wt%.

[0021] Furthermore, the specific surface area of the catalyst for hydrogenation and capture of silicon and phosphorus is 250m 2 / g~320m 2 / g, pore volume is 0.4cm 3 ·g -1 ~0.7cm 3 ·g -1 ;

[0022] Preferably, the average pore size of the hydrogenation silicon-phosphorus capture catalyst is 9 nm to 11 nm;

[0023] Preferably, the proportion of pores with a diameter of 4 nm to 10 nm in the hydrogenation silicon-phosphorus capture catalyst is 65% to 85%.

[0024] Furthermore, the L acid content in the hydrogenation silicon phosphorus capture catalyst is 0.150 mmol·g -1 ~0.350mmol·g -1 , B acid content is 0.002mmol·g -1 ~0.005mmol·g -1 , the total acid content is 0.152mmol·g -1 ~0.355mmol·g -1 .

[0025] In a second aspect, a method for preparing the catalyst for hydrogenation and capture of silicon and phosphorus as described in any one of the above items comprises the following steps:

[0026] The carrier is impregnated with molybdenum salt and nickel salt by saturated impregnation to obtain a catalyst precursor. The catalyst precursor is calcined and then impregnated with silica sol by unsaturated impregnation and calcined to obtain the hydrogenation silicon-phosphorus capture catalyst.

[0027] Furthermore, the preparation method of the carrier comprises the following steps:

[0028] Organic acid iron salt and organic acid are mixed and dissolved to form a solution, pseudo-boehmite and an extrusion aid are mixed and added into the solution, and the carrier is obtained by extrusion molding and calcination.

[0029] Furthermore, the organic acid iron salt includes at least one of ferric citrate, ferrous oxalate, ferrous acetate, ferric tartrate and ferrous gluconate, preferably ferric citrate and / or ferrous oxalate;

[0030] Preferably, the organic acid comprises at least one of oxalic acid, citric acid, tartaric acid, p-toluenesulfonic acid, ethylenediaminetetraacetic acid and glutamic acid, preferably oxalic acid and / or citric acid;

[0031] Preferably, the specific surface area of the pseudo-boehmite is 300m 2 / g~380m 2 / g, preferably 320m 2 / g~360m 2 / g;

[0032] Preferably, the pore volume of the pseudo-boehmite is 0.90 cm 3 ·g -1 ~1.20cm 3 ·g -1 , preferably 0.95cm 3 ·g -1 ~1.15cm3 ·g -1 ;

[0033] Preferably, the extrusion aid comprises at least one of sesbania powder, hydroxypropyl methylcellulose, carboxymethyl cellulose and polyethylene glycol, preferably sesbania powder and / or carboxymethyl cellulose;

[0034] Preferably, the molybdenum salt comprises ammonium molybdate;

[0035] Preferably, the nickel salt includes at least one of nickel nitrate, nickel sulfate and nickel acetate, preferably nickel nitrate.

[0036] In a third aspect, a catalyst for hydrogenation and capture of silicon and phosphorus as described in any one of the above items is used for hydrogenation and removal of silicon and phosphorus from distillate oil feedstock.

[0037] Compared with the prior art, the present invention has at least the following beneficial effects:

[0038] The catalyst for hydrogenation and capture of silicon and phosphorus provided by the present invention has nickel and molybdenum in the catalyst serving as active centers for silicon capture, and iron serving as active centers for phosphorus capture. The catalyst can simultaneously remove silicon and phosphorus impurities from distillate oil feedstock, and is a dual-function catalyst. Furthermore, the catalyst introduces silicon dioxide, i.e., silica sol (nanoscale acidic silica), to increase the L acid content in the catalyst. L acid facilitates the breaking of silicon-oxygen and phosphorus-oxygen bonds, forming small molecules of silicon-phosphorus compounds that facilitate adsorption and capture. Nanoscale silica sol particles can partially enter the pore structure, thereby increasing the specific surface area of the catalyst while also improving the crushing strength of the catalyst.

[0039] The preparation method of the catalyst for hydrogenation and capture of silicon and phosphorus provided by the present invention has a simple process, is easy to operate, and has a high success rate. Silica sol is introduced by an unsaturated impregnation method, and the formed catalyst has a core-shell structure, so that the surface layer of the catalyst is acidic silica sol, which is beneficial to improving the adsorption and capture and fixation effect of silicon and phosphorus impurities.

[0040] The application of the hydrogenation silicon-phosphorus capture catalyst provided by the present invention can effectively remove silicon and phosphorus impurities in the distillate oil raw material, thereby protecting the main catalyst from poisoning and deactivation, which is beneficial to extending the service life of the catalyst and protecting the long-term stable operation of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0042] Figure 1 This is a SEM-EDS scanning photograph of the catalyst obtained in Test Example 2 of the present invention. DETAILED DESCRIPTION

[0043] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0044] According to a first aspect of the present invention, there is provided a catalyst for hydrogenating silicon and phosphorus, mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0045] The nickel oxide in the catalyst accounts for 1 wt% to 6 wt%, and its typical but non-limiting proportion is, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 6 wt%. The molybdenum trioxide accounts for 4 wt% to 9 wt%, and its typical but non-limiting proportion is, for example, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, and 9 wt%. The silicon dioxide accounts for 0.1 wt% to 0.7 wt%, and its typical but non-limiting proportion is, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, and 0.7 wt%.

[0046] The carrier contains aluminum oxide, carbon and ferrous oxide;

[0047] The ferrous oxide accounts for 0.2 wt% to 3 wt% in the catalyst, and typical but non-limiting proportions include 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 2 wt%, and 3 wt%.

[0048] The nickel and molybdenum in the catalyst of the present invention can serve as active centers for silicon capture, and the iron can serve as active centers for phosphorus capture. The catalyst can simultaneously remove silicon and phosphorus impurities in distillate oil raw materials and is a dual-function catalyst. The catalyst of the present invention introduces silicon dioxide, namely silica sol (nanoscale acidic silica), which, on the one hand, can increase the L acid content in the catalyst. The L acid is conducive to the breaking of silicon-oxygen bonds and phosphorus-oxygen bonds, forming small molecules of silicon-phosphorus compounds that are easy to adsorb and capture. On the other hand, the nanoscale silica sol particles can partially enter the pore structure, thereby increasing the specific surface area of the catalyst while also improving the crushing strength of the catalyst.

[0049] In a preferred embodiment, the nickel oxide content in the catalyst may be 2 wt% to 5 wt%.

[0050] In a preferred embodiment, the molybdenum trioxide content in the catalyst may be 5 wt% to 9 wt%.

[0051] In a preferred embodiment, the proportion of silicon dioxide in the catalyst may be 0.2 wt% to 0.5 wt%.

[0052] In a preferred embodiment, the ferrous oxide content in the catalyst may be 0.5 wt% to 2 wt%.

[0053] In the present invention, the proportion of alumina in the carrier can be 83wt% to 92wt%, and its typical but non-limiting proportions are, for example, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, and 92wt%. The proportion of carbon can be 2wt% to 4wt%, and its typical but non-limiting proportions are, for example, 2wt%, 3wt%, and 4wt%.

[0054] In a preferred embodiment, the specific surface area of the catalyst of the present invention can be 250m 2 / g~320m 2 / g, with a typical but non-limiting specific surface area of 250 m 2 / g, 260m 2 / g, 270m 2 / g, 280m 2 / g, 290m 2 / g、300m 2 / g、310m 2 / g、320m 2 / g, the pore volume can be 0.4cm 3 ·g -1 ~0.7cm 3 ·g -1 , with a typical but non-limiting pore volume of, for example, 0.4 cm 3 ·g -1 , 0.5cm 3 ·g -1 , 0.6cm 3 ·g -1 , 0.7cm 3 ·g -1 .

[0055] In a preferred embodiment, the average pore diameter of the catalyst of the present invention may be 9 nm to 11 nm, and typical but non-limiting average pore diameters are, for example, 9 nm, 10 nm, and 11 nm.

[0056] In a preferred embodiment, the proportion of pores with a diameter of 4 nm to 10 nm in the catalyst of the present invention may be 65% to 85%, with typical but non-limiting proportions being, for example, 65%, 70%, 75%, 80%, and 85%.

[0057] In a preferred embodiment, the L acid content in the catalyst of the present invention can be 0.150 mmol·g -1 ~0.350mmol·g -1 , a typical but non-limiting content thereof is, for example, 0.150 mmol·g -1 , 0.200mmol·g -1 , 0.250mmol·g -1 、0.300mmol·g -1 、0.350mmol·g -1 , the B acid content can be 0.002mmol·g -1 ~0.005mmol·g -1 , a typical but non-limiting content thereof is, for example, 0.002 mmol·g -1 , 0.003mmol·g -1 , 0.004mmol·g -1 , 0.005mmol·g -1 , the total acid content can be 0.152mmol·g -1 ~0.355mmol·g -1 .

[0058] With the coordinated coordination of various specific parameters, the catalyst of the present invention can effectively remove silicon and phosphorus from distillate oils such as coker gasoline, coker diesel, straight-run naphtha and straight-run diesel. Under typical process conditions, the removal rate of silicon and phosphorus in distillate oils can reach more than 95%, thereby effectively protecting the main catalyst from poisoning and deactivation.

[0059] According to a second aspect of the present invention, there is provided a method for preparing any one of the above-mentioned catalysts for hydrogenating silicon and phosphorus, comprising the following steps:

[0060] The carrier is impregnated with molybdenum salt and nickel salt by saturated impregnation to obtain a catalyst precursor. The catalyst precursor is calcined and then impregnated with silica sol by unsaturated impregnation and calcined to obtain a hydrogenation silicon-phosphorus capture catalyst.

[0061] The preparation method of the catalyst of the present invention is simple in process, easy to operate and has a high success rate. The silica sol is introduced by an unsaturated impregnation method, and the formed catalyst has a core-shell structure, so that the surface layer of the catalyst is acidic silica sol, which is beneficial to improving the adsorption and capture and fixation effect of silicon and phosphorus impurities.

[0062] It should be noted that the catalyst uses an unsaturated impregnation method to introduce silica sol, so that the catalyst forms a core-shell structure. The surface layer of the catalyst is acidic silica sol. The increase in specific surface area is conducive to the adsorption of silicon and phosphorus impurities. After adsorption, they enter the internal pore structure and are captured and fixed at the active center. At the same time, small molecular impurities such as sulfur and nitrogen will also enter the internal pores of the catalyst to react and be removed.

[0063] In a preferred embodiment, the method for preparing the catalyst support comprises the following steps:

[0064] Organic acid iron salt and organic acid are mixed and dissolved to form a solution, pseudo-boehmite and an extrusion aid are mixed and added into the solution, and the carrier is obtained by extrusion molding and calcination.

[0065] A typical preparation method of a catalyst for hydrogenating silicon and phosphorus capture comprises the following steps:

[0066] (1) dissolving an organic acid iron salt and an organic acid in deionized water to form a solution;

[0067] (2) After the pseudo-boehmite powder and the extrusion aid are uniformly mixed, the mixture is added to the solution of step (1) and further mixed, and then extruded through a twin-screw extruder. The extrusion template selected can be clover-shaped to obtain a shaped carrier;

[0068] (3) placing the formed carrier from step (2) in a blast drying oven for drying, and then crushing and screening the carrier after drying to ensure that the proportion of carriers with a length of 2 mm to 8 mm is not less than 95%;

[0069] placing the crushed and screened carrier in a tube furnace for calcination to obtain a catalyst carrier;

[0070] (4) dissolving the molybdenum salt and the nickel salt in deionized water to prepare a metal salt solution according to the mass and saturated water absorption of the catalyst support in step (3);

[0071] The catalyst support of step (3) is impregnated with a metal salt solution by saturation impregnation to complete the impregnation of molybdenum salt and nickel salt to obtain a catalyst precursor;

[0072] (5) drying the catalyst precursor obtained in step (4) in a forced air drying oven, and then calcining the catalyst precursor in a tubular furnace to obtain a semi-finished catalyst;

[0073] (6) dissolving the silica sol in deionized water to prepare a silica sol solution based on the mass and saturated water absorption of the semi-finished catalyst in step (5);

[0074] The semi-finished catalyst of step (5) is impregnated with a silica sol solution by unsaturated impregnation to complete the impregnation of the silica sol (i.e., silicon dioxide) to obtain a semi-finished catalyst impregnated with silica sol;

[0075] (7) The semi-finished catalyst obtained in step (6) is placed in a blast drying oven for drying. After drying, it is placed in a tubular furnace for roasting to obtain a finished catalyst, that is, a hydrogenation silicon-phosphorus capture catalyst.

[0076] In the present invention, the organic acid iron salt includes but is not limited to at least one of ferric citrate, ferrous oxalate, ferrous acetate, ferric tartrate and ferrous gluconate, and may be further preferably ferric citrate and / or ferrous oxalate; the organic acid includes but is not limited to at least one of oxalic acid, citric acid, tartaric acid, p-toluenesulfonic acid, ethylenediaminetetraacetic acid and glutamic acid, and may be further preferably oxalic acid and / or citric acid.

[0077] In a preferred embodiment, the specific surface area of pseudo-boehmite can be 300m 2 / g~380m 2 / g, with a typical but non-limiting specific surface area of, for example, 300 m 2 / g、320m 2 / g、340m 2 / g、360m 2 / g、380m 2 / g, and more preferably 320m 2 / g~360m 2 / g.

[0078] In a preferred embodiment, the pore volume of pseudo-boehmite can be 0.90 cm 3 ·g -1 ~1.20cm 3 ·g -1 , with a typical but non-limiting pore volume of, for example, 0.90 cm 3 ·g -1 , 0.95cm 3 ·g -1 , 1.00cm 3 ·g -1 , 1.05cm 3 ·g -1 、1.10cm 3 ·g -1 , 1.15cm 3 ·g -1 , 1.20cm 3 ·g -1 , which may be further preferably 0.95cm 3 ·g -1 ~1.15cm3 ·g -1 .

[0079] In a preferred embodiment, the extrusion aid includes but is not limited to at least one of sesbania powder, hydroxypropyl methylcellulose, carboxymethyl cellulose and polyethylene glycol, and may further preferably be sesbania powder and / or carboxymethyl cellulose.

[0080] It should be noted that the amount of the extrusion aid can account for 1% to 5% of the mass of the pseudo-boehmite powder, for example, 1%, 2%, 3%, 4%, 5%, but not limited thereto, and can be further preferably 3% to 4%.

[0081] In the present invention, the molybdenum salt includes but is not limited to ammonium molybdate, for example, it can be at least one of ammonium molybdate monohydrate, ammonium molybdate trihydrate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate, and is more preferably ammonium heptamolybdate.

[0082] In the present invention, the nickel salt includes but is not limited to at least one of nickel nitrate, nickel sulfate and nickel acetate, and is more preferably nickel nitrate.

[0083] In step (3) of the present invention, the drying temperature of the molded carrier can be 100°C to 150°C, and typical but non-limiting drying temperatures are, for example, 100°C, 110°C, 120°C, 130°C, 140°C, and 150°C, and may be further preferably 110°C to 130°C. The drying time of the molded carrier can be 2 hours to 8 hours, and typical but non-limiting drying times are, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, and 8 hours, and may be further preferably 3 hours to 5 hours. The carrier calcination temperature can be 550°C. The calcination temperature is preferably 550-650°C, and typical but non-limiting temperatures include 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, and 650°C, and may be further preferably 580-620°C. The calcination atmosphere may be nitrogen or an inert gas atmosphere, and may be further preferably nitrogen or argon. The calcination time may be 2 hours to 6 hours, and typical but non-limiting times include 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, and may be further preferably 3 hours to 5 hours.

[0084] In step (5) of the present invention, the drying temperature of the catalyst precursor can be 100°C to 150°C, and typical but non-limiting drying temperatures are, for example, 100°C, 110°C, 120°C, 130°C, 140°C, and 150°C, and may be further preferably 110°C to 130°C. The drying time of the catalyst precursor can be 2 hours to 8 hours, and typical but non-limiting drying times are, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, and 8 hours, and may be further preferably 3 hours to 5 hours. The calcination time of the catalyst precursor is 1 hour to 8 hours. The temperature can be 380°C to 550°C, and typical but non-limiting temperatures include 380°C, 390°C, 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, and 550°C, and can be further preferably 400°C to 500°C. The calcination atmosphere can be nitrogen or an inert gas atmosphere, and can be further preferably nitrogen or argon. The calcination time can be 2 hours to 6 hours, and typical but non-limiting times include 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, and can be further preferably 3 hours to 5 hours.

[0085] In a preferred embodiment, the silica sol may be at least one of neutral silica sol, acidic silica sol and alkaline silica sol, and may be more preferably acidic silica sol.

[0086] In the present invention, the particle size of the silica sol can be 1 nm to 10 nm, and its typical but non-limiting particle size is, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, and 10 nm, and can be further preferably 1 nm to 5 nm. The saturated water absorption ratio can range from 10% to 30%, for example, 10%, 20%, and 30%, but is not limited thereto, and can be further preferably 10% to 20%.

[0087] In step (7) of the present invention, the drying temperature of the catalyst can be 100°C to 150°C, and typical but non-limiting drying temperatures are, for example, 100°C, 110°C, 120°C, 130°C, 140°C, and 150°C, and may be further preferably 110°C to 130°C. The drying time of the catalyst can be 2 hours to 8 hours, and typical but non-limiting drying times are, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, and 8 hours, and may be further preferably 3 hours to 5 hours. The temperature of the catalyst calcination can be 200°C. The calcination temperature is 200-300°C, and typical but non-limiting temperatures include 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, and 300°C, and may be further preferably 200-250°C. The calcination atmosphere may be nitrogen or an inert gas atmosphere, and may be further preferably nitrogen or argon. The calcination time may be 2 hours to 6 hours, and typical but non-limiting times include 2 hours, 3 hours, 4 hours, 5 hours, and 6 hours, and may be further preferably 3 hours to 5 hours.

[0088] According to a third aspect of the present invention, there is provided a use of any of the above-mentioned catalysts for hydrogenating silicon and phosphorus for removing silicon and phosphorus from distillate oil feedstock.

[0089] The use of the catalyst of the present invention in the hydrogenation removal of silicon and phosphorus from distillate oil raw materials comprises the following steps:

[0090] (1) The catalyst was subjected to sulfurization treatment. 3 wt% DMDS was added to straight-run kerosene to prepare sulfurized oil. The temperature was raised to 150°C at a heating rate of 20°C / h, kept constant at that temperature for 2 hours, and then sulfurized oil was added. The temperature was raised to 200°C at 10°C / h and kept constant at that temperature for 2 hours. The temperature was then raised to 230°C at 10°C / h and kept constant at that temperature for 8 hours. The temperature was then raised to 320°C at 10°C / h and kept constant at that temperature for 8 hours. The sulfurization was completed.

[0091] Among them, the sulfidation pressure is 4Mpa~8Mpa, the hydrogen-oil ratio is 500:1~800:1, and the volume space velocity is 2h -1 ~4h -1 ;

[0092] (2) The catalyst is shallowly reduced before use, and hydrogen is introduced at 200°C to 350°C, preferably 200°C to 300°C, with a hydrogen flow rate of 1 L·h -1 ·g -1 ~3L·h -1 ·g -1 Catalyst, preferably 1 L·h -1 ·g -1 ~2L·h -1 ·g -1 catalyst;

[0093] The reduction time is 12 to 48 hours, preferably 12 to 24 hours.

[0094] (3) The reaction conditions for the catalyst application are as follows:

[0095] Reaction pressure 1Mpa~10Mpa, preferably 2Mpa~8Mpa;

[0096] Reaction temperature 180°C to 380°C, preferably 220°C to 360°C;

[0097] Volume space velocity 0.5h -1 ~7h -1 , preferably 0.5h -1 ~5h -1 ;

[0098] The volume ratio of hydrogen to oil is 50:1 to 1000:1, preferably 100:1 to 800:1.

[0099] The application of the hydrogenation silicon-phosphorus capture catalyst provided by the present invention can effectively remove silicon and phosphorus impurities in the distillate oil raw material, thereby protecting the main catalyst from poisoning and deactivation, which is beneficial to extending the service life of the catalyst and protecting the long-term stable operation of the device.

[0100] The present invention is further described below by way of examples. Unless otherwise specified, the materials in the examples were prepared according to existing methods or directly purchased from the market.

[0101] Example 1

[0102] A catalyst for hydrogenating silicon and phosphorus, mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0103] The catalyst contains 2 wt% nickel oxide, 5 wt% molybdenum trioxide, and 0.2 wt% silicon dioxide.

[0104] The carrier contains alumina (γ-Al2O3), carbon and ferrous oxide;

[0105] The ferrous oxide content in the catalyst is 1.5 wt%.

[0106] In this embodiment, the method for preparing the catalyst comprises the following steps:

[0107] (1) Weigh 5.11 g of ferric citrate and 3.75 g of oxalic acid into a beaker, dilute to 127.5 mL with deionized water, and stir thoroughly until completely dissolved; weigh 150 g of pseudo-boehmite powder, add 4.5 g of sesbania powder, and mix thoroughly; pour the solution prepared in the first step into the mixed powder, further stir evenly, and use a twin-screw extruder to extrude the clover leaf as a template to form the shaped carrier; place the formed carrier in a blast drying oven, dry at 120 ° C for 3 hours, crush and sieve, place in a tubular furnace, and calcine at 580 degrees for 3 hours under a nitrogen atmosphere to complete the preparation of the catalyst carrier;

[0108] (2) Weigh 7.94 g of nickel nitrate hexahydrate and 6.19 g of ammonium molybdate tetrahydrate into a beaker, add deionized water to make the volume 72 mL, and stir until the metal salt is completely dissolved to prepare an impregnation solution; weigh 90 g of a carrier, use a saturated impregnation method to impregnate the metal salt solution onto the weighed carrier, place it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120° C. for 3 hours, place it in a tube furnace, and calcine it at 450° C. under a nitrogen atmosphere for 3 hours to prepare a catalyst precursor;

[0109] (3) Weigh 50 g of catalyst precursor for use, weigh 0.67 g of 30% silica sol and add it to a beaker, prepare an impregnation solution based on 20% of the water absorption rate of the catalyst precursor, dilute the volume to 6 mL with deionized water, and use an unsaturated impregnation method to impregnate the silica sol impregnation solution onto the catalyst precursor. After leaving it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120°C for 3 hours, place it in a tubular furnace, and calcine it at 210°C under a nitrogen atmosphere for 3 hours to obtain a hydrogenated silicon-phosphorus capture catalyst, which is recorded as CHJ-1.

[0110] Example 2

[0111] A catalyst for hydrogenating silicon and phosphorus, mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0112] The catalyst contains 2 wt% nickel oxide, 5 wt% molybdenum trioxide, and 0.2 wt% silicon dioxide.

[0113] The carrier contains alumina (γ-Al2O3), carbon and ferrous oxide;

[0114] The ferrous oxide content in the catalyst is 0.5 wt%.

[0115] In this embodiment, the method for preparing the catalyst comprises the following steps:

[0116] (1) Weigh 1.00 g of ferrous oxalate and 5.25 g of citric acid into a beaker, dilute to 127.5 mL with deionized water, and stir thoroughly until completely dissolved; weigh 150 g of pseudo-boehmite powder, add 6 g of sesbania powder, mix thoroughly, pour the solution prepared in the first step into the mixed powder, further stir evenly, use a twin-screw extruder, extrude and mold using clover as a template, place the molded carrier in a blast drying oven, dry at 130 ° C for 4 hours, crush and sieve, place in a tube furnace, and calcine at 600 degrees for 4 hours under an argon atmosphere to complete the preparation of the catalyst carrier;

[0117] (2) Weigh 7.94 g of nickel nitrate hexahydrate and 6.19 g of ammonium molybdate tetrahydrate into a beaker, add deionized water to the volume to 72 mL, and stir until the metal salt is completely dissolved to prepare an impregnation solution; weigh 90 g of a carrier, use a saturated impregnation method to impregnate the metal salt solution onto the weighed carrier, place it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 130°C for 4 hours, place it in a tube furnace, and calcine it at 500°C under an argon atmosphere for 3.5 hours to prepare a catalyst precursor;

[0118] (3) Weigh 50 g of catalyst precursor for use, weigh 0.67 g of 30% silica sol and add it to a beaker, prepare an impregnation solution based on 15% of the water absorption rate of the catalyst precursor, dilute the volume to 4.5 mL with deionized water, and use an unsaturated impregnation method to impregnate the silica sol impregnation solution onto the catalyst precursor. After standing at room temperature for 3 hours, place it in a forced drying oven, dry it at 130°C for 4 hours, place it in a tubular furnace, and calcine it at 230°C under an argon atmosphere for 4 hours to obtain a hydrogenated silicon-phosphorus capture catalyst, which is recorded as CHJ-2.

[0119] Example 3

[0120] A catalyst for hydrogenating silicon and phosphorus, mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0121] The catalyst contains 3 wt% nickel oxide, 7 wt% molybdenum trioxide, and 0.2 wt% silicon dioxide.

[0122] The carrier contains alumina (γ-Al2O3), carbon and ferrous oxide;

[0123] The ferrous oxide content in the catalyst is 1.5 wt%.

[0124] In this embodiment, the method for preparing the catalyst comprises the following steps:

[0125] (1) Weigh 5.11 g of ferric citrate and 3.75 g of oxalic acid into a beaker, dilute to 127.5 mL with deionized water, and stir thoroughly until completely dissolved; weigh 150 g of pseudo-boehmite powder, add 4.5 g of sesbania powder, and mix thoroughly; pour the solution prepared in the first step into the mixed powder, further stir evenly, and use a twin-screw extruder to extrude the clover leaf as a template to form the shaped carrier; place the formed carrier in a blast drying oven, dry at 120 ° C for 3 hours, crush and sieve, place in a tubular furnace, and calcine at 580 degrees for 3 hours under a nitrogen atmosphere to complete the preparation of the catalyst carrier;

[0126] (2) Weigh 11.92 g of nickel nitrate hexahydrate and 8.67 g of ammonium molybdate tetrahydrate into a beaker, add deionized water to make the volume 72 mL, and stir until the metal salt is completely dissolved to prepare an impregnation solution; weigh 90 g of a carrier, use a saturated impregnation method to impregnate the metal salt solution onto the weighed carrier, place it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120° C. for 3 hours, place it in a tube furnace, and calcine it at 450° C. under a nitrogen atmosphere for 3 hours to prepare a catalyst precursor;

[0127] (3) Weigh 50 g of catalyst precursor for use, weigh 0.67 g of 30% silica sol and add it to a beaker, prepare an impregnation solution based on 20% of the water absorption rate of the catalyst precursor, dilute to 6 mL with deionized water, and use an unsaturated impregnation method to impregnate the silica sol impregnation solution onto the catalyst precursor. After standing at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120°C for 3 hours, place it in a tubular furnace, and calcine it at 210°C under a nitrogen atmosphere for 3 hours to obtain a hydrogenated silicon-phosphorus capture catalyst, which is recorded as CHJ-3.

[0128] Example 4

[0129] A catalyst for hydrogenating silicon and phosphorus, mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and a carrier;

[0130] The catalyst contains 2 wt% nickel oxide, 5 wt% molybdenum trioxide, and 0.5 wt% silicon dioxide.

[0131] The carrier contains alumina (γ-Al2O3), carbon and ferrous oxide;

[0132] The ferrous oxide content in the catalyst is 1.5 wt%.

[0133] In this embodiment, the method for preparing the catalyst comprises the following steps:

[0134] (1) Weigh 5.11 g of ferric citrate and 3.75 g of oxalic acid into a beaker, dilute to 127.5 mL with deionized water, and stir thoroughly until completely dissolved; weigh 150 g of pseudo-boehmite powder, add 4.5 g of sesbania powder, and mix thoroughly; pour the solution prepared in the first step into the mixed powder, further stir evenly, and use a twin-screw extruder to extrude the clover leaf as a template to form the shaped carrier; place the formed carrier in a blast drying oven, dry at 120 ° C for 3 hours, crush and sieve, place in a tubular furnace, and calcine at 580 degrees for 3 hours under a nitrogen atmosphere to complete the preparation of the catalyst carrier;

[0135] (2) Weigh 11.92 g of nickel nitrate hexahydrate and 8.67 g of ammonium molybdate tetrahydrate into a beaker, add deionized water to make the volume 72 mL, and stir until the metal salt is completely dissolved to prepare an impregnation solution; weigh 90 g of a carrier, use a saturated impregnation method to impregnate the metal salt solution onto the weighed carrier, place it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120° C. for 3 hours, place it in a tube furnace, and calcine it at 450° C. under a nitrogen atmosphere for 3 hours to prepare a catalyst precursor;

[0136] (3) Weigh 50 g of catalyst precursor for use, weigh 1.67 g of 30% silica sol and add it to a beaker, prepare an impregnation solution based on 30% of the water absorption rate of the catalyst precursor, dilute the volume to 9 mL with deionized water, and use an unsaturated impregnation method to impregnate the silica sol impregnation solution onto the catalyst precursor. After leaving it at room temperature for 3 hours, place it in a forced air drying oven, dry it at 120°C for 3 hours, place it in a tubular furnace, and calcine it at 210°C under a nitrogen atmosphere for 3 hours to obtain a hydrogenated silicon-phosphorus capture catalyst, which is recorded as CHJ-4.

[0137] Comparative Example 1

[0138] The only difference between this comparative example and Example 1 is that no silica sol is impregnated in step (3);

[0139] The remaining steps and process parameters were the same as those in Example 1 to obtain a catalyst, which was designated as DCHJ-1.

[0140] Comparative Example 2

[0141] The only difference between this comparative example and Example 1 is that no iron source is added in step (1);

[0142] The remaining steps and process parameters were the same as those in Example 1 to obtain a catalyst, which was designated as DCHJ-2.

[0143] Comparative Example 3

[0144] The only difference between this comparative example and Example 1 is that the silica sol is impregnated by saturated impregnation, that is, in step (3), 50 g of catalyst precursor is weighed for standby use, 0.67 g of 30% silica sol is weighed and added to a beaker, an impregnation solution is prepared based on 100% water absorption of the catalyst precursor, the volume is fixed to 30 mL with deionized water, and the silica sol impregnation solution is impregnated on the catalyst precursor by saturated impregnation. After being placed at room temperature for 3 hours, the silica sol impregnation solution is placed in a forced drying oven, dried at 120° C. for 3 hours, placed in a tube furnace, and calcined at 210° C. under a nitrogen atmosphere for 3 hours;

[0145] The remaining steps and process parameters were the same as those in Example 1 to obtain a catalyst, which was designated as DCHJ-3.

[0146] Test Example 1

[0147] The physicochemical properties of the catalysts obtained in Examples 1-4 and Comparative Examples 1-3 are shown in Table 1.

[0148] Table 1

[0149] project CHJ-1 CHJ-2 CHJ-3 CHJ-4 DCHJ-1 DCHJ-2 DCHJ-3 <![CDATA[Specific surface area / m 2 ·g -1 > 295 283 272 304 281 291 261 <![CDATA[Pore volume / cm 3 ·g -1 > 0.53 0.57 0.52 0.60 0.58 0.62 0.50 Most probable pore diameter / nm 8.65 9.32 7.86 9.23 6.59 8.59 6.12 <![CDATA[B acid / mmol·g -1 > 0.003 0.004 0.003 0.005 0.002 0.003 0.004 <![CDATA[L acid / mmol·g -1 > 0.154 0.200 0.155 0.342 0.150 0.153 0.347 <![CDATA[Total acid content / mmol·g -1 > 0.157 0.204 0.158 0.347 0.152 0.156 0.351 <![CDATA[Measuring pressure strength / N·mm -1 > 15 13 17 19 11 14 20

[0150] It can be seen from the data in Table 1 that the introduction of silica increases the specific surface area of the catalyst, increases the content of L-acid in the catalyst, and improves the crushing strength of the catalyst.

[0151] Test Example 2

[0152] Coker gasoline and straight-run diesel were used as feedstock oils. The properties of the feedstock oils are shown in Table 2. Hexamethylcyclotrisiloxane was used as a silicon source, and tributyl phosphate was used as a phosphorus source. These were added simultaneously to the feedstock oils to ensure that the silicon and phosphorus contents in the coker gasoline and straight-run diesel were both around 50 ppm. Due to weighing errors, the silicon and phosphorus contents were subject to actual analysis.

[0153] The catalyst was tested for desiliconization / phosphorus activity and silicon / phosphorus capacity using a 100 mL fixed-bed hydrogenation apparatus. 50 mL of catalyst and 50 mL of quartz sand were weighed, mixed evenly, and densely packed in the constant temperature section of the reactor. The catalyst was sulfided and reduced before the reaction.

[0154] The catalyst vulcanization process is as follows: 5 kg of straight-run kerosene is weighed, mixed with 154 g of DMDS to make vulcanized oil, poured into the vulcanization tank, and the reactor is heated to 150 ° C at a heating rate of 20 ° C / h, kept at this temperature for 2 hours, and then the vulcanized oil is added. The temperature is raised to 200 ° C at 10 ° C / h and kept at this temperature for 2 hours, then raised to 230 ° C at 10 ° C / h and kept at this temperature for 8 hours, and then raised to 320 ° C at 10 ° C / h and kept at this temperature for 8 hours, and the vulcanization is completed. Among them, the vulcanization pressure is 5 MPa, the hydrogen-to-oil ratio is 600:1, and the volume space velocity is 4 h -1 ;

[0155] After the sulfidation is completed, the catalyst is shallowly reduced, mainly to reduce the ferrous oxide in the active component of the catalyst to improve the phosphorus capture activity. The reduction process is as follows: hydrogen is introduced at 220 ° C, and the hydrogen flow rate is 2 L·h -1 ·g -1 Catalyst, reduction time is 36 hours;

[0156] After the sulfidation and reduction are completed, the catalyst performance evaluation test begins;

[0157] (1) Catalyst silicon capture / phosphorus capture activity evaluation test

[0158] The catalyst evaluation test conditions were as follows: reaction pressure 2.5 MPa, reaction temperature 280 °C, volume space velocity 5 h -1 The hydrogen-to-oil volume ratio is 100:1. The catalyst evaluation test conditions are as follows: reaction pressure 7 MPa, reaction temperature 320 ° C, volume space velocity 2 h -1 , the volume ratio of hydrogen to oil is 600:1;

[0159] The evaluation results are shown in Table 3 (using coker gasoline as the feedstock oil) and Table 4 (using straight-run diesel as the feedstock oil);

[0160] (2) Catalyst silicon capacity / phosphorus capacity evaluation test

[0161] The silicon and phosphorus content of the catalyst were determined using straight-run diesel added with silicon source and phosphorus source as raw materials. The test conditions were as follows: reaction pressure 7 MPa, reaction temperature 320 °C, volume space velocity 2 h -1 The volume ratio of hydrogen to oil is 600:1. Samples are taken for analysis every 24 hours during the test. When the silicon content or phosphorus content in the product is the same as that in the feed oil, the test is stopped, the catalyst is disassembled, and the silicon or phosphorus content captured in the catalyst is analyzed, which is the silicon capacity or phosphorus capacity of the catalyst.

[0162] The evaluation results are shown in Table 5.

[0163] Table 2

[0164] project Coking gasoline straight-run diesel <![CDATA[Sulfur content / μg·g -1 > 3210 1820 <![CDATA[Nitrogen content / μg·g -1 > 261 165 <![CDATA[Silicon content / μg·g -1 > 51 53 <![CDATA[Phosphorus content / μg·g -1 > 50 52

[0165] Table 3

[0166] project CHJ-1 CHJ-2 CHJ-3 CHJ-4 DCHJ-1 DCHJ-2 DCHJ-3 <![CDATA[Sulfur content of gasoline products / μg·g -1 > 1620 1580 1512 1585 1682 1520 1729 <![CDATA[Nitrogen content of gasoline product / μg·g -1 > 142 131 118 133 153 138 159 <![CDATA[Silicon content in gasoline products / μg·g -1 > 2.8 2.5 3 2 6.9 4.3 5.9 <![CDATA[Phosphorus content of gasoline products / μg·g -1 > 2 3.6 2.4 2.1 7.3 12.8 6.2 Desiliconization rate / wt% 94.5 95.1 94.1 96.1 86.5 91.6 88.4 Dephosphorization rate / wt% 96 92.8 95.2 95.8 85.4 74.4 87.6

[0167] Table 4

[0168] project CHJ-1 CHJ-2 CHJ-3 CHJ-4 DCHJ-1 DCHJ-2 DCHJ-3 <![CDATA[Sulfur content of diesel products / μg·g -1 > 1020 985 982 993 1053 986 1127 <![CDATA[Nitrogen content of diesel products / μg·g -1 > 95 89 82 95 109 92 118 <![CDATA[Silicon content in diesel products / μg·g -1 > 2.7 2.6 3.1 2.2 7.1 4.4 5.7 <![CDATA[Diesel product phosphorus content / μg·g -1 > 1.9 3.7 2.3 2 7.2 13.8 6.5 Desiliconization rate / wt% 94.7 94.9 93.9 95.7 86.1 91.4 88.8 Dephosphorization rate / wt% 96.2 92.6 95.4 96 85.6 72.4 87

[0169] Table 5

[0170] project CHJ-1 CHJ-2 CHJ-3 CHJ-4 DCHJ-1 DCHJ-2 DCHJ-3 Silicon content / wt% 21.5 23.6 21.3 25.3 23.8 25.5 19.8 Phosphorus content / wt% 22.7 24.7 22.4 26.3 24.9 26.7 20.3

[0171] It can be seen from the data in Tables 2, 3, 4 and 5 that CHJ-1 to CHJ-4 can all effectively remove silicon and phosphorus impurities from distillate oil. The addition of silica effectively improves the desiliconization and denitrification performance of the catalyst. However, the introduction of silica by the saturated impregnation method will reduce the pore volume of the catalyst, resulting in a decrease in the silicon capacity and phosphorus capacity. At the same time, without the addition of iron additive, the dephosphorization activity of the catalyst will be greatly reduced.

[0172] Scanning electron microscopy morphology analysis and energy spectrum element (SEM-EDS) detection can give the spatial distribution of catalyst components and reveal the uniformity and dispersion of catalyst components; Figure 1 The SEM-EDS scanning photo of the catalyst shows that the silica introduced by unsaturated impregnation is mainly concentrated in the outer layer of the catalyst, so that the catalyst has a core-shell structure. The external acidity and macroporous structure are conducive to the bond breaking and capture of large molecules such as siloxanes and phospholipids in the distillate oil, and also make it easier for small sulfur and nitrogen molecules to enter the internal pores of the catalyst for reaction and removal, which effectively improves the performance of the catalyst.

[0173] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A catalyst for hydrogenating silicon and phosphorus, characterized in that: Mainly composed of nickel oxide, molybdenum trioxide, silicon dioxide and carrier; The nickel oxide in the catalyst accounts for 1 wt% to 6 wt%, the molybdenum trioxide accounts for 4 wt% to 9 wt%, and the silicon dioxide accounts for 0.1 wt% to 0.7 wt%; The carrier contains aluminum oxide, carbon and ferrous oxide; The ferrous oxide accounts for 0.2 wt% to 3 wt% in the catalyst.

2. The catalyst according to claim 1, characterized in that The nickel oxide content in the catalyst is 2 wt% to 5 wt%; Preferably, the molybdenum trioxide content in the catalyst is 5 wt% to 9 wt%; Preferably, the content of silicon dioxide in the catalyst is 0.2 wt% to 0.5 wt%.

3. The catalyst according to claim 1, characterized in that The ferrous oxide accounts for 0.5 wt% to 2 wt% in the catalyst.

4. The catalyst according to any one of claims 1 to 3, characterized in that The carrier contains 83 wt% to 92 wt% of alumina and 2 wt% to 4 wt% of carbon.

5. The catalyst according to claim 4, characterized in that The specific surface area of the catalyst is 250 m 2 / g~320m 2 / g, pore volume is 0.4cm 3 ·g -1 ~0.7cm 3 ·g -1 ; Preferably, the average pore size of the catalyst is 9 nm to 11 nm; Preferably, the proportion of pores with a diameter of 4 nm to 10 nm in the catalyst is 65% to 85%.

6. The catalyst according to claim 4, characterized in that The L acid content in the catalyst is 0.150 mmol·g -1 ~0.350mmol·g -1 , B acid content 0.002mmol·g -1 ~0.005mmol·g -1 , total acid content 0.152mmol·g -1 ~0.355mmol·g -1 .

7. A method for preparing the catalyst according to any one of claims 1 to 6, characterized in that: The following steps are involved: The carrier is impregnated with molybdenum salt and nickel salt by saturated impregnation to obtain a catalyst precursor. The catalyst precursor is calcined and then impregnated with silica sol by unsaturated impregnation and calcined to obtain the hydrogenation silicon-phosphorus capture catalyst.

8. The preparation method according to claim 7, characterized in that The preparation method of the carrier comprises the following steps: Organic acid iron salt and organic acid are mixed and dissolved to form a solution, pseudo-boehmite and an extrusion aid are mixed and added into the solution, and the carrier is obtained by extrusion molding and calcination.

9. The preparation method according to claim 8, characterized in that The organic acid iron salt includes at least one of ferric citrate, ferrous oxalate, ferrous acetate, ferric tartrate and ferrous gluconate, preferably ferric citrate and / or ferrous oxalate; Preferably, the organic acid comprises at least one of oxalic acid, citric acid, tartaric acid, p-toluenesulfonic acid, ethylenediaminetetraacetic acid and glutamic acid, preferably oxalic acid and / or citric acid; Preferably, the specific surface area of the pseudo-boehmite is 300m 2 / g~380m 2 / g, preferably 320m 2 / g~360m 2 / g; Preferably, the pore volume of the pseudo-boehmite is 0.90 cm 3 ·g -1 ~1.20cm 3 ·g -1 , preferably 0.95cm 3 ·g -1 ~1.15cm 3 ·g -1 ; Preferably, the extrusion aid comprises at least one of sesbania powder, hydroxypropyl methylcellulose, carboxymethyl cellulose and polyethylene glycol, preferably sesbania powder and / or carboxymethyl cellulose; Preferably, the molybdenum salt comprises ammonium molybdate; Preferably, the nickel salt includes at least one of nickel nitrate, nickel sulfate and nickel acetate, preferably nickel nitrate.

10. Use of the catalyst for hydrogenation silicon and phosphorus capture according to any one of claims 1 to 6 in hydrogenation removal of silicon and phosphorus from distillate oil feedstock.

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