A hydrogenation silicon capture catalyst and its preparation method and application

Abstract

A hydrogenation silicon capture catalyst comprising alumina and an active component, wherein, based on the total weight of the catalyst, the metal oxide of Group VIB is 2-20%, the metal oxide of Group VIII is 1-10%, and the specific surface area is 300-500m 2 / g, with a surface hydroxyl content of 800-2000µmol / g. After sulfurization, TEM analysis revealed 3-5 stacking layers of Group VIB metal sulfides, and a 2-5nm crystal length. An alumina precursor is mixed with an organic additive and a metal salt solution, and a peptizing agent and water are added. The mixture is extruded to form a silicon capture catalyst. The organic additive adsorbs on the surface of the alumina precursor, blocking the interaction between the metal salt and the alumina. This creates an alumina precursor / organic additive / metal salt sandwich structure in the mixed system, which blocks contact between the alumina particles, hindering the aggregation and growth of the alumina and increasing the specific surface area. This increased exposure of the alumina increases the catalyst's surface hydroxyl content, thereby improving the silicon-holding capacity of the hydrogenation silicon capture catalyst.

Description

Technical Field

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

[0002] Currently, my country still has a large number of delayed coking units processing heavy, low-quality oil. Defoamers are used during this process, resulting in a certain amount of silicon in products such as coker dry gas, coker naphtha, and coker diesel. This silicon poisons the catalysts used in subsequent coking product processing, leading to permanent catalyst deactivation. Therefore, the hydroprocessing of coker dry gas, coker naphtha, and coker diesel requires the installation of silicon-capturing catalysts.

[0003] CN201911020761.2 discloses a silicon scavenger and a preparation method thereof. The silicon scavenger of the present invention comprises a carrier and a hydrogenation active component, wherein the hydrogenation active component is a Group VIB metal sulfide, a Group VIB metal oxide, and a Group VIII metal oxide. Based on the total weight of the silicon scavenger, the Group VIB metal sulfide is 0.3wt%-18.3wt%, the Group VIB metal oxide is 0.1wt%-5.0wt%, and the Group VIII metal oxide is 0.2wt%-12.0wt%. The preparation method of the silicon scavenger of the present invention comprises the following steps: (1) impregnating a catalyst carrier with an impregnation solution containing a Group VIB metal, followed by drying, and sulfurizing the dried material; (2) impregnating the sulfurized material in step (1) with an impregnation solution containing Group VIB and Group VIII metals, followed by drying and calcining under an inert atmosphere to obtain the silicon scavenger.

[0004] CN200910188090.0 discloses a coking naphtha silicon scavenger and its application. The coking naphtha silicon scavenger uses alumina as a carrier, silicon dioxide as an auxiliary agent, and W, Mo, and Ni as hydrogenation components. The pore volume of the coking naphtha silicon scavenger is 0.5-0.70 ml / g, and the specific surface area is 250-500 m 2 / g, the content of hydrogenated components is 1% to 20% calculated as oxides, and the acid content is 0.3 to 0.5 mmol / g.

[0005] The silicon-capturing catalyst of the above-mentioned invention patent is prepared by impregnating active metal into alumina or modified alumina carrier. The alumina or modified alumina carrier needs to be calcined at high temperature, resulting in loss of specific surface area and reducing the silicon holding capacity of the silicon-capturing catalyst. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the present invention starts from the silicon capture mechanism of the silicon capture catalyst and prepares a hydrogenation silicon capture catalyst by increasing the specific surface area and surface hydroxyl content of the silicon capture catalyst. The catalyst has high silicon holding capacity and low cost.

[0007] In the context of this specification, FTIR (infrared spectroscopy) was used to analyze the hydroxyl content of the catalyst. The FTIR test conditions included grinding the catalyst, pressing it into a 13 mm diameter self-supporting sheet, and placing it on the in-situ cell sample holder. The experiment used a Nicolet 6700 Fourier transform infrared spectrometer with 32 scans, a resolution of 4 cm-1, and a range of 4000 to 650 cm-1. -1 The detector was MCT / A. All infrared experimental results were normalized according to the catalyst mass. TEM (high-resolution transmission electron microscopy) was used to analyze the morphological characteristics of the active metal after sulfidation. The TEM test conditions include: the electron gun type is LaB6, the acceleration voltage is 200kV, the point resolution is 0.23nm, the line resolution is 0.14nm, the sample is placed on the sample stage for testing, and the number and length of the lamellae on at least 20 TEM images are counted. Then, the average length of the VIB group metal sulfide lamellae is calculated according to the following calculation formulas (1) and (2) respectively ( ) and the average number of stacked layers ( The TEM analysis was performed on the hydrogenation catalyst after sulfidation (referred to as the sulfided hydrogenation catalyst). The sulfidation conditions included sulfidation at 320°C with 30 mL / min of H2S for 2 hours.

[0008]

[0009] In formulas (1) and (2), Platelets m length; The length is The total number of lamellae; Platelets m The number of stacking layers; The number of layers is The number of platelets; k is the total number of stripes in the statistical area.

[0010] In order to achieve the above technical objectives, the technical solutions of the present invention are as follows:

[0011] The technical purpose of the first aspect of the present invention is to provide a hydrogenation silicon capture catalyst, comprising alumina and an active component, wherein the active component is a Group VIB metal oxide and a Group VIII metal oxide, and based on the total weight of the catalyst, the Group VIB metal oxide is 2-20%, preferably 3-13%, and the Group VIII metal oxide is 1-10%, preferably 2-5%; the specific surface area of ​​the hydrogenation silicon capture catalyst is 300-500m 2 / g, preferably 350-450m 2 / g; the surface hydroxyl content is 800-2000µmol / g, preferably 1000-1600µmol / g, and most preferably 1000-1400µmol / g; after the hydrogenation silicon capture catalyst is sulfurized, when TEM analysis is performed, the number of stacking layers of the VIB Group metal sulfide is 3-5 layers, and the crystal length of the VIB Group metal sulfide is 2-5nm.

[0012] Furthermore, the vulcanization is dry vulcanization or wet vulcanization. The vulcanizing agent for dry vulcanization is hydrogen sulfide, and the vulcanizing agent for wet vulcanization is one or two selected from carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide; the vulcanization pressure is 2.0-6.4 MPa, the vulcanization temperature is 250-400° C., and the vulcanization time is 4-12 hours.

[0013] Furthermore, the Group VIB metal oxide is molybdenum oxide and / or tungsten oxide, and the Group VIII metal oxide is nickel oxide and / or cobalt oxide.

[0014] The technical purpose of the second aspect of the present invention is to provide a method for preparing the above-mentioned hydrogenation silicon capture catalyst, comprising the following steps:

[0015] (1) Alumina precursor and an organic additive are uniformly mixed, and then a mixed solution of a Group VIB metal salt and a Group VIII metal salt is added to obtain a catalyst precursor; the particle size of the aluminum oxide precursor is 1-500 nm, preferably 10-200 nm;

[0016] (2) Adding a peptizing agent and water to the catalyst precursor of step (1), mixing them evenly, and then extruding and molding them to obtain a silicon capture catalyst.

[0017] Furthermore, the uniform mixing in step (1) is to mix the raw materials by any solid material mixing means available in the prior art to achieve a degree of sufficient mixing recognized by those skilled in the art.

[0018] Furthermore, the precursor of the aluminum oxide in step (1) is selected from one or more of pseudo-boehmite, boehmite, gibbsite, nordstromite and diaspore.

[0019] Furthermore, the Group VIB metal salt in step (1) is a phosphate and / or an ammonium salt. The concentration of the Group VIB metal salt solution, calculated as metal oxide, is 0.1 g / mL to 2 g / mL.

[0020] Furthermore, the Group VIII metal salt in step (1) is selected from one or more of nitrates, carbonates, phosphates, sulfates, basic carbonates, and acetates. The concentration of the Group VIII metal salt, calculated as metal oxide, is 0.1 g / mL to 3 g / mL.

[0021] Furthermore, the organic additive in step (1) is an alcohol or organic acid having 3 to 10 carbon atoms and containing a hydroxyl group and / or a carboxyl group. Specifically, it is at least one selected from ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, malonic acid, succinic acid, and glutaric acid. The amount of the organic additive added is 5 to 20 wt %, preferably 8 to 15 wt %, of the alumina precursor, calculated as alumina.

[0022] Furthermore, the peptizing agent in step (2) is well known to those skilled in the art. As a more specific embodiment, the peptizing agent is selected from at least one of nitric acid, phosphoric acid and acetic acid.

[0023] Furthermore, the aluminum oxide precursor is calculated as aluminum oxide, and the amount of the peptizing agent added is 1-8 wt %, preferably 2-5 wt % of the aluminum oxide; and the amount of water added is 30-120 wt %, preferably 50-100 wt % of the aluminum oxide.

[0024] Furthermore, step (2) further includes a drying process after extrusion molding, and the drying conditions are: drying temperature 90-500°C, preferably 100-400°C, and drying time 1-10 hours, preferably 3-6 hours.

[0025] The third aspect of the present invention provides a method for applying the hydrogenation silicon-capturing catalyst to the hydrogenation treatment of silicon-containing oils. The silicon-capturing catalyst requires vulcanization prior to application, with either dry or wet vulcanization being the preferred method. The dry vulcanizing agent is hydrogen sulfide, while the wet vulcanizing agent is one or two of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide. The vulcanization pressure is 2.0-6.4 MPa, the temperature is 250-400°C, and the time is 4-12 hours.

[0026] Compared with the prior art, the catalyst of the present invention has the following advantages:

[0027] (1) The silicon capture catalyst of the present invention is prepared by first mixing a solid alumina precursor and an organic additive, then uniformly mixing the mixture with an active metal salt solution, and then adding a peptizing agent and water to knead and form the mixture. The organic additive will be adsorbed on the surface of the alumina precursor, acting as a barrier layer, and then mixed with the active metal salt solution. The organic additive can block the interaction between the metal salt and the alumina. At the same time, since the active metal salt is in an ionic state and the particles are very small, when the two are mixed, a sandwich structure of alumina precursor / organic additive / metal salt will be formed, which blocks the contact of the alumina particles, thereby hindering the aggregation and growth of alumina, increasing the specific surface area, and at the same time blocking the loss of the alumina specific surface area caused by the peptizing agent, and also contributing to increasing the specific surface area of ​​the catalyst to a certain extent.

[0028] (2) A sandwich structure of alumina precursor / organic additive / metal salt is formed. When treated at a certain temperature, the outermost metal salt first interacts with each other to form metal oxide particles, thereby exposing the alumina and increasing the exposed surface of the alumina, thereby increasing the surface hydroxyl content of the catalyst, thereby improving the silicon capacity of the hydrogenation silicon capture catalyst.

[0029] (3) In addition, the preparation process of the present invention is simple, which greatly reduces the preparation cost of the catalyst and improves the competitiveness of the catalyst.

[0030] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0031] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0032] The present invention uses FTIR (infrared spectroscopy) to analyze the hydroxyl content of the catalyst. The FTIR test conditions include: after the catalyst is ground, pressed into a Φ13 mm self-supporting sheet, and placed on the in-situ cell sample holder. The experiment uses a Nicolet 6700 Fourier transform infrared spectrometer with 32 scans and a resolution of 4 cm -1 , 4000~650cm -1 All infrared experimental results were normalized according to the catalyst mass.

[0033] The present invention uses N2-adsorption / desorption to analyze the specific surface area of ​​the silicon capture agent. The N2-adsorption / desorption test conditions are as follows: the catalyst is loaded into a sample tube, and the ASAP 2420 nitrogen physical adsorption instrument from MICROMERITICS, USA, is used to perform N2 adsorption and desorption tests at a temperature of 77K.

[0034] The present invention uses TEM (high-resolution transmission electron microscopy) to analyze the morphological characteristics of active metals after sulfidation. The TEM test conditions include: the electron gun type is LaB6, the acceleration voltage is 200kV, the point resolution is 0.23nm, and the line resolution is 0.14nm. The sample is placed on the sample stage for testing, and the number and length of the lamellae on at least 20 TEM images are counted. Then, the average length of the VIB group metal sulfide lamellae is calculated according to the following calculation formulas (1) and (2), respectively ( ) and the average number of stacked layers ( The TEM analysis was performed on the hydrogenation catalyst after sulfidation (referred to as the sulfided hydrogenation catalyst). The sulfidation conditions included sulfidation at 320°C with 30 mL / min of H2S for 2 hours.

[0035]

[0036] In formulas (1) and (2), Platelets m length; The length is The total number of lamellae; Platelets m The number of stacking layers; The number of layers is The number of platelets; k is the total number of stripes in the statistical area.

[0037] Example 1

[0038] (1) Glycerol and pseudo-boehmite with a particle size of 5-10 nm are mixed evenly, and then mixed evenly with a solution containing ammonium heptamolybdate and nickel nitrate, where the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide. The weight ratio of each component is m(molybdenum oxide):m(nickel oxide):m(aluminum oxide):m(glycerol) = 10.3:3.6:86.1:10, to obtain a catalyst precursor;

[0039] (2) Nitric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of nitric acid added is 3.5% of the alumina and the amount of water added is 95% of the alumina. After mixing evenly, the mixture is extruded and then treated at 400°C for 3 hours to obtain the silicon capture catalyst FS-1.

[0040] The weight percentages of the components in the silicon capture catalyst FS-1 are: MoO3 is 10.3%, NiO is 3.6%, and the rest is alumina.

[0041] Example 2

[0042] (1) Mixing citric acid and pseudo-boehmite with a particle size of 20-30 nm, and then mixing them with a solution containing ammonium heptamolybdate and cobalt nitrate, wherein the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, and the weight ratio of each component is m (molybdenum oxide): m (cobalt oxide): m (aluminum oxide): m (citric acid) = 9.9:4.1:86:12, to obtain a catalyst precursor;

[0043] (2) Phosphoric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of phosphoric acid added is 4.5% of the alumina and the amount of water added is 100% of the alumina. After mixing evenly, the mixture is extruded and then treated at 350°C for 3 hours to obtain the silicon capture catalyst FS-2.

[0044] The weight percentages of the components in the silicon capture catalyst FS-2 are: MoO3 is 9.9%, CoO is 4.1%, and the rest is alumina.

[0045] Example 3

[0046] (1) isobutanol is mixed evenly with pseudo-boehmite having a particle size of 20-30 nm, and then mixed evenly with a solution containing ammonium heptamolybdate, cobalt nitrate, and nickel nitrate, wherein the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, wherein the weight ratio of each component is m(molybdenum oxide):m(nickel oxide):m(cobalt oxide):m(aluminum oxide):m(isobutanol) = 10.3:2.2:2.1:85.4:15, to obtain a catalyst precursor;

[0047] (2) Nitric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of nitric acid added is 2.5% of the alumina and the amount of water added is 105% of the alumina. After mixing evenly, the mixture is extruded and then treated at 400°C for 3 hours to obtain a silicon capture catalyst FS-3.

[0048] The weight percentages of the components in the silicon capture catalyst FS-3 are: MoO3 is 10.3%, NiO is 2.2%, CoO is 2.1%, and the rest is alumina.

[0049] Example 4

[0050] (1) isobutanol is mixed evenly with pseudo-boehmite having a particle size of 20-30 nm, and then mixed evenly with a solution containing ammonium tungstate and nickel nitrate, wherein the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, wherein the weight ratio of each component is m(molybdenum oxide):m(nickel oxide):m(aluminum oxide):m(isobutanol) = 12.5:2.6:84.9:15, to obtain a catalyst precursor;

[0051] (2) Phosphoric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of phosphoric acid added is 3.5% of the alumina and the amount of water added is 115% of the alumina. After mixing evenly, the mixture is extruded and then treated at 350°C for 3 hours to obtain the silicon capture catalyst FS-4.

[0052] The weight percentages of the components in the silicon capture catalyst FS-4 are: WO3 is 12.5%, NiO is 2.6%, and the rest is alumina.

[0053] Example 5

[0054] (1) Acetic acid and boehmite with a particle size of 20-30 nm are mixed evenly, and then mixed evenly with a solution containing ammonium tungstate and cobalt nitrate, where the active metal is calculated as oxide and the boehmite is calculated as aluminum oxide, and the weight ratio of each component is m(molybdenum oxide):m(cobalt oxide):m(aluminum oxide):m(acetic acid) = 11.4:3.8:84.8:10, to obtain a catalyst precursor;

[0055] (2) Phosphoric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of phosphoric acid added is 4.5% of the alumina and the amount of water added is 105% of the alumina. After mixing evenly, the mixture is extruded and then treated at 330°C for 3 hours to obtain the silicon capture catalyst FS-5.

[0056] The weight percentages of the components in the silicon capture catalyst FS-5 are: WO3 is 11.4%, CoO is 3.8%, and the rest is alumina.

[0057] Example 6

[0058] (1) Succinic acid and pseudo-boehmite with a particle size of 20-30 nm are mixed evenly, and then mixed evenly with a solution containing ammonium tungstate, nickel nitrate and cobalt nitrate, where the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, wherein the weight ratio of each component is m(tungsten oxide):m(nickel oxide):m(cobalt oxide):m(aluminum oxide):m(succinic acid) = 13.2:2.1:2.6:82.1:12, to obtain a catalyst precursor;

[0059] (2) Phosphoric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of phosphoric acid added is 3.5% of the alumina and the amount of water added is 85% of the alumina. After mixing evenly, the mixture is extruded and then treated at 380°C for 3 hours to obtain the silicon capture catalyst FS-6.

[0060] The weight percentages of the components in the silicon capture catalyst FS-6 are: WO3 is 13.2%, NiO is 2.1%, CoO is 2.6%, and the rest is alumina.

[0061] Example 7

[0062] (1) Mixing citric acid and pseudo-boehmite with a particle size of 20-30 nm, and then mixing them with a solution containing ammonium tungstate, ammonium heptamolybdate and nickel nitrate, wherein the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, wherein the weight ratio of each component is m(molybdenum oxide):m(tungsten oxide):m(nickel oxide):m(aluminum oxide):m(citric acid) = 7.1:5.6:3.2:84.1:10, to obtain a catalyst precursor;

[0063] (2) Phosphoric acid and water are uniformly added to the catalyst precursor of step (1), wherein the amount of phosphoric acid added is 4.5% of the alumina and the amount of water added is 95% of the alumina. After mixing evenly, the mixture is extruded and then treated at 380°C for 3 hours to obtain the silicon capture catalyst FS-7.

[0064] The weight percentages of the components in the silicon capture catalyst FS-7 are: MoO3 is 7.1%, WO3 is 5.6%, NiO is 3.2%, and the rest is alumina.

[0065] Comparative Example 1

[0066] (1) dissolving ammonium heptamolybdate and nickel nitrate in water to form a metal salt solution, and then uniformly mixing the solution with pseudo-boehmite having a particle size of 5-10 nm, wherein the active metal is calculated as oxide and the pseudo-boehmite is calculated as aluminum oxide, and the weight ratio of the components is m (molybdenum oxide): m (nickel oxide): m (aluminum oxide) = 10.3:3.6:86.1, to obtain a catalyst precursor;

[0067] The operation process of step (2) is the same as that of Example 1 to obtain a comparative silicon capture catalyst DC-1.

[0068] The weight percentages of the components in the comparative silicon capture catalyst DC-1 are as follows: MoO3 is 10.3%, NiO is 3.6%, and the rest is alumina.

[0069] Comparative Example 2

[0070] (1) Pseudoboehmite, nitric acid, and deionized water were uniformly mixed, wherein the mass ratio of pseudoboehmite: nitric acid: deionized water was 100:3.5:90, and then kneaded and extruded into strips, and then dried at 120°C for 10 hours and calcined at 700°C for 3 hours to obtain an alumina carrier.

[0071] (2) The ammonium heptamolybdate and nickel nitrate solution were impregnated into the alumina carrier prepared in step (1), and then dried at 90°C for 3 hours and calcined at 450°C for 3 hours to obtain the silicon capture catalyst DC-2.

[0072] The weight percentages of the components in the comparative silicon capture catalyst DC-2 are as follows: MoO3 is 10.3%, NiO is 3.6%, and the rest is alumina.

[0073] Comparative Example 3

[0074] (1) Pseudoboehmite, phosphoric acid, and deionized water were mixed uniformly, wherein the mass ratio of pseudoboehmite: phosphoric acid: deionized water was 100:4.5:95, and then kneaded and extruded into strips, and then dried at 110°C for 10 hours and calcined at 750°C for 3 hours to obtain an alumina carrier.

[0075] (2) The ammonium heptamolybdate and cobalt nitrate solution was impregnated into the alumina support prepared in step (1), and then dried at 110°C for 3 hours and calcined at 350°C for 3 hours to obtain the silicon capture catalyst DC-3.

[0076] The weight percentages of the components in the comparative silicon capture catalyst DC-3 are as follows: MoO3 is 9.7%, CoO is 3.1%, and the rest is alumina.

[0077] Comparative Example 4

[0078] (1) Ammonium heptamolybdate and nickel nitrate were dissolved in deionized water and then mixed evenly with pseudo-boehmite with a particle size of 5-10 nm, propylene glycol, nitric acid, and deionized water. The active metals were calculated as oxides and the pseudo-boehmite was calculated as aluminum oxide. The weight ratio of each component was m(molybdenum oxide):m(nickel oxide):m(aluminum oxide):m(propylene glycol):m(nitric acid):m(water)=10.3:3.6:86.1:10:3:90. The mixture was extruded and then treated at 400°C for 3 hours to obtain a comparative silicon capture catalyst DC-4.

[0079] The weight percentages of the components in the comparative silicon capture catalyst DC-4 are as follows: MoO3 is 10.3%, NiO is 3.6%, and the rest is alumina.

[0080] Comparative Example 5

[0081] (1) Glycerol and pseudo-boehmite with a particle size of 600-800 nm are mixed evenly, and then mixed evenly with a solution containing ammonium heptamolybdate and nickel nitrate, with the active metal being calculated as oxide and the pseudo-boehmite being calculated as aluminum oxide. The weight ratio of the components is m(molybdenum oxide):m(nickel oxide):m(aluminum oxide):m(glycerol) = 10.3:3.6:86.1:10, to obtain a catalyst precursor;

[0082] The operation process of step (2) is the same as that of Example 1 to obtain a comparative silicon capture catalyst DC-5.

[0083] The weight percentages of the components in the comparative silicon capture catalyst DC-5 are as follows: MoO3 is 10.3%, NiO is 3.6%, and the rest is alumina.

[0084] The physicochemical properties of the catalysts FS-1 to FS-7 prepared in the above examples and the catalysts DC-1 to DC-4 prepared in the comparative examples were analyzed. The analysis results are shown in Table 1.

[0085] Table 1.

[0086]

[0087] Example 8

[0088] This example illustrates the silicon capture activity of the catalyst provided by the present invention for coker naphtha.

[0089] The raw oil used for evaluation is coking naphtha provided by a refinery of Sinopec, and its main properties are as follows: sulfur content is 2856μg / g, nitrogen content is 62μg / g, and silicon content is 205μg / g. A 200mL fixed bed hydrogenation device was used to evaluate the silicon capture capacity of silicon capture catalysts FS-1 to FS-7 and comparative examples DC-1 to DC-4. Among them, silicon capture catalysts FS-1 to FS-7 and comparative examples DC-1 to DC-4 were pre-sulfurized. The pre-sulfurization conditions are: using aviation kerosene containing 1.5wt% CS2 at an air velocity of 1.5h -1 The presulfidation was carried out at an operating pressure of 4.0 MPa, a hydrogen / oil volume ratio of 500:1, and an operating pressure of 4.0 MPa. The evaluation reaction conditions were: operating pressure 3.0 MPa, reaction temperature 280°C, hydrogen / oil volume ratio 300:1, and volume space velocity 2.0 h -1 After running for 300 hours, the silicon scavenger was unloaded and then calcined at 500℃ for 3 hours. The SiO2 content in the silicon scavenger was analyzed by XRF. The evaluation results are shown in Table 2.

[0090] Table 2.

[0091]

[0092] As can be seen from Table 2, the silicon-capturing catalyst of the present invention has a very high silicon-holding capacity.

Claims

1. A hydrogenation silicon capture catalyst, characterized in that: The catalyst comprises aluminum oxide and an active component, wherein the active component is a metal oxide of Group VIB and a metal oxide of Group VIII. Based on the total weight of the catalyst, the metal oxide of Group VIB accounts for 2-20%, and the metal oxide of Group VIII accounts for 1-10%. The specific surface area of ​​the hydrogenation silicon capture catalyst is 300-500m 2 / g, a surface hydroxyl content of 800-2000 μmol / g, and after the hydrogenation silicon capture catalyst is sulfurized, when analyzed by TEM, the number of stacking layers of the VIB group metal sulfide is 3-5 layers, and the crystal length of the VIB group metal sulfide is 2-5 nm; The silicon capture catalyst is prepared by the following steps: (1) uniformly mixing an alumina precursor with an organic additive, wherein the organic additive is an alcohol and / or an organic acid having 3 to 10 carbon atoms, and then adding a mixed solution of a Group VIB metal salt and a Group VIII metal salt to obtain a catalyst precursor; the particle size of the alumina precursor is 1 to 500 nm; (2) Adding a peptizing agent and water to the catalyst precursor of step (1), mixing them evenly, extruding and molding them, and drying them to obtain a silicon capture catalyst.

2. The silicon-trapping catalyst according to claim 1, characterized in that The Group VIB metal oxide is molybdenum oxide and / or tungsten oxide, and the Group VIII metal oxide is nickel oxide and / or cobalt oxide.

3. The method for preparing the silicon-trapping catalyst according to claim 1, comprising the following steps: (1) uniformly mixing an alumina precursor with an organic additive, wherein the organic additive is an alcohol and / or an organic acid having 3 to 10 carbon atoms, and then adding a mixed solution of a Group VIB metal salt and a Group VIII metal salt to obtain a catalyst precursor; the particle size of the alumina precursor is 1 to 500 nm; (2) Adding a peptizing agent and water to the catalyst precursor of step (1), mixing them evenly, extruding and molding them, and drying them to obtain a silicon capture catalyst.

4. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The particle size of the aluminum oxide precursor in step (1) is 10-200 nm.

5. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The precursor of aluminum oxide in step (1) is selected from one or more of pseudo-boehmite, boehmite, gibbsite, nordstromite and diaspore.

6. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The Group VIB metal salt in step (1) is a phosphate and / or an ammonium salt. In the mixed solution, the concentration of the Group VIB metal salt, calculated as metal oxide, is 0.1 g / mL to 2 g / mL.

7. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The Group VIII metal salt in step (1) is selected from one or more of nitrates, carbonates, phosphates, sulfates, basic carbonates and acetates. The concentration of the Group VIII metal salt in the mixed solution, calculated as metal oxide, is 0.1 g / mL to 3 g / mL.

8. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The organic auxiliary agent is selected from at least one of glycerol, butylene glycol, pentanediol, citric acid, malonic acid, succinic acid and glutaric acid.

9. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The alumina precursor is calculated on the basis of alumina, and the amount of the organic additive added is 5-20 wt % of the alumina.

10. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The peptizing agent is selected from at least one of nitric acid, phosphoric acid and acetic acid.

11. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The aluminum oxide precursor is calculated as aluminum oxide, and the amount of the peptizing agent added is 1-8 wt % of the aluminum oxide.

12. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The amount of water added in step (2) is 30-120 wt% of the alumina.

13. The method for preparing a silicon-trapping catalyst according to claim 3, wherein: The drying conditions in step (2) are: drying temperature 90-500°C, and drying time 1-10 hours.

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