Hydrogenation catalyst, and preparation method therefor and use thereof

Abstract

A hydrogenation catalyst, and a preparation method therefor and a use thereof. The hydrogenation catalyst comprises a carrier, an active component, and N-graphdiyne. The active component is loaded on the carrier, and the N-graphdiyne is loaded on the carrier or is mixed in the carrier; the carrier comprises an aluminum oxide-lanthanum oxide-titanium oxide composite carrier; the active component is selected from at least two sulfides in metal M; the metal M is selected from group VIII and group VIB; and based on the total mass of the hydrogenation catalyst, the content of N-graphdiyne in the hydrogenation catalyst is 0.01-5 wt%. By using the aluminum oxide-lanthanum oxide-titanium oxide composite carrier as a composite carrier and introducing N-graphdiyne, the hydrogenation catalyst has high hydrodesulfurization and denitrification activity.

Description

Hydrogenation catalyst and its preparation method and application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application No. 202310855021.0 filed on July 12, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the field of petroleum refining, and in particular to a hydrogenation catalyst and a preparation method and application thereof. Background Art

[0004] At present, hydrodesulfurization is the main method to reduce the sulfur content in distillate oil raw materials. Hydrodesulfurization, hydrodenitrogenation, olefin saturation and other reactions can be carried out simultaneously to produce clean oil products or their blending components.

[0005] The China VI standard for automotive gasoline and diesel requires that the sulfur content of hydrogenated products be no greater than 10 mg / kg. Therefore, hydrodesulfurization activity is the most critical indicator for hydrogenation catalysts. Furthermore, although the nitrogen content in low-quality distillates is lower than the sulfur content, nitrogen compounds can significantly impact the stability of the oil product, strongly inhibiting the removal of sulfides. In particular, basic nitrogen compounds are more susceptible to adsorption on the acidic sites of the catalyst and are difficult to desorb. This directly leads to a decrease in the number of active sites, affecting the catalyst's activity and lifespan, leading to catalyst poisoning and deactivation, and ultimately affecting the quality of the hydrogenated product. Therefore, reducing nitrogen compounds in the distillate is crucial for improving hydrodesulfurization reaction activity.

[0006] The catalyst prepared by using mesoporous magnesium oxide loaded with Co and Mo in CN103157518A has high catalytic activity for the hydrodesulfurization reaction of dibenzothiophene compounds. However, the stability of the magnesium oxide support is significantly different from that of the aluminum oxide support, the hydrogenation activity is not high, and the preparation route is complex, making it difficult to operate on industrial equipment.

[0007] In order to improve the activity of the catalyst, CN1052501A adds additives P, F, and B to an impregnation solution containing the three metals Co-W-Mo. The catalyst is impregnated by a staged impregnation method, and the finished catalyst is obtained after drying and calcination. After impregnation and loading of the active metal, the catalyst is subjected to high-temperature calcination. The interaction between the active metal components and the carrier is strong, which affects the sulfurization effect of the catalyst and also causes some active metal components to aggregate, affecting the dispersion of the active metal and thus the activity of the catalyst.

[0008] The hydrogenation catalyst in CN102851061A uses Si-modified alumina and ETS-10 titanium silicalite with a grain size of less than 2 μm as a carrier, with Fe, Co, Ni, Mo, and W as active components. This catalyst can reduce the sulfur content, nitrogen content, and olefin content of low-quality gasoline to below 50 μg / g, below 50 μg / g, and below 30 vol.%, with an octane loss of less than 3 units. It can also process high-sulfur diesel, reducing the sulfur content to below 50 μg / g and the nitrogen content to below 20 μg / g, with a diesel yield exceeding 99.8 wt.%. However, the microporous structure of the ETS-10 molecular sieve is not conducive to the reaction of large molecular sulfur and nitrogen compounds, and its hydrogenation activity needs to be improved.

[0009] In summary, there is an urgent need for a hydrogenation catalyst with high hydrodesulfurization activity and a simple preparation method.

[0010] Summary of the Invention

[0011] The purpose of the present invention is to overcome the problem of low desulfurization and denitrification activity of hydrogenation catalysts in the prior art and to provide a hydrogenation catalyst and a preparation method and application thereof.

[0012] In order to achieve the above object, the present invention provides a hydrogenation catalyst in a first aspect, wherein the hydrogenation catalyst comprises: a carrier, an active component and N-graphene; wherein the active component is supported on the carrier, and the N-graphene is supported on the carrier or mixed in the carrier;

[0013] Wherein, the carrier comprises an aluminum oxide-lanthanum oxide-titanium oxide composite carrier;

[0014] Wherein, the active component is selected from sulfides of at least two metals M;

[0015] wherein the metal M is selected from Group VIII and Group VIB;

[0016] Wherein, based on the total mass of the hydrogenation catalyst, the content of N-graphene in the hydrogenation catalyst is 0.01-5wt%.

[0017] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, wherein the preparation method comprises the following steps:

[0018] (1) treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, an extrusion aid, and a binder to obtain a carrier;

[0019] (2) mixing an aqueous solution containing an active component precursor and N-graphene to obtain a dispersion, wherein the active component precursor is a compound of at least two selected from metals M;

[0020] (3) immersing the support in the dispersion, drying, and calcining to obtain a hydrogenation catalyst precursor;

[0021] or:

[0022] A. treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, N-graphene, an extrusion aid, and a binder to obtain a base material;

[0023] B. mixing aqueous solutions containing active component precursors to obtain an impregnation solution, wherein the active component precursors are selected from compounds of at least two of the metals M;

[0024] C. Immersing the base material in an impregnation solution, drying, and calcining to obtain a hydrogenation catalyst precursor;

[0025] wherein the metal M is selected from Group VIII and Group VIB;

[0026] The amount of N-graphene used is such that the content of N-graphene in the prepared hydrogenation catalyst is 0.01-5 wt % based on the total amount of the hydrogenation catalyst;

[0027] The preparation method further comprises sulfiding the hydrogenation catalyst precursor to obtain the hydrogenation catalyst.

[0028] The third aspect of the present invention provides a hydrogenation catalyst prepared by the above preparation method.

[0029] A fourth aspect of the present invention provides use of the above hydrogenation catalyst in petroleum refining.

[0030] Through the above technical solution, the hydrogenation catalyst provided by the present invention and its preparation method and application achieve the following beneficial effects:

[0031] (1) In the present invention, the hydrogenation catalyst uses an alumina-lanthanum oxide-titanium oxide composite support as a composite support, which weakens the interaction between the support and the active component and can further enhance the hydrogenation activity of the hydrogenation catalyst.

[0032] (2) In the present invention, the introduction of N-graphene into the hydrogenation catalyst helps to form a highly dispersed active phase, inhibits agglomeration during high temperature, and then accurately regulates the structure of the hydrogenation active phase to form a highly dispersed type II phase hydrogenation active center, which significantly improves the hydrogenation activity of the catalyst. The hydrogenation catalyst has high hydrodesulfurization and denitrification activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] FIG1 is a BET diagram of the hydrogenation catalyst of Example 1;

[0034] FIG2 is a TEM image of the hydrogenation catalyst of Example 1. DETAILED DESCRIPTION

[0035] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0036] A first aspect of the present invention provides a hydrogenation catalyst, wherein the hydrogenation catalyst comprises: a carrier, an active component and N-graphene; wherein the active component is supported on the carrier, and the N-graphene is supported on the carrier or mixed in the carrier;

[0037] Wherein, the carrier comprises an aluminum oxide-lanthanum oxide-titanium oxide composite carrier;

[0038] Wherein, the active component is selected from sulfides of at least two metals M;

[0039] wherein the metal M is selected from Group VIII and Group VIB;

[0040] Wherein, based on the total mass of the hydrogenation catalyst, the content of N-graphene in the hydrogenation catalyst is 0.01-5wt%.

[0041] In the present invention, the hydrogenation catalyst uses an aluminum oxide-lanthanum oxide-titanium oxide composite carrier as a composite carrier, which weakens the interaction between the carrier and the active component, improves the dispersion of the active metal, and can further enhance the hydrogenation activity of the hydrogenation catalyst.

[0042] In the present invention, N-graphyne can serve as a carrier or attachment site for active metals, physically isolating active sites and improving the dispersion of the active phase. At the same time, N-graphyne has a unique electronic structure that can achieve rapid electron transfer, facilitate hydrogen overflow, enhance the synergistic effect between active metal sites, and thus improve catalyst activity.

[0043] In the present invention, N-graphene helps to form a highly dispersed active phase, inhibits agglomeration during high-temperature processes, and then precisely regulates the structure of the hydrogenation active phase to form highly dispersed type II phase hydrogenation active centers, significantly improving the hydrogenation activity of the catalyst. The hydrogenation catalyst has high hydrodesulfurization and denitrification activity.

[0044] According to the present invention, preferably, based on the total mass of the hydrogenation catalyst, the content of N-graphyne in the hydrogenation catalyst is 0.1-5 wt%, more preferably 0.1-3 wt%, and even more preferably 0.5-3 wt%.

[0045] In the present invention, when the content of N-graphene is 0.1-3 wt%, the hydrodesulfurization and denitrification performance is even better.

[0046] In the present invention, the introduction of titanium oxide in the alumina-lanthanum oxide-titania composite carrier improves the hydrodesulfurization and denitrification performance of the hydrogenation catalyst. Specifically, titanium oxide has a variable valence state, which can adjust the surface properties of the carrier, change the distribution and chemical state of the active components, and enhance the hydrogen overflow activity.

[0047] According to the present invention, based on the total mass of the hydrogenation catalyst, the content of lanthanum oxide in the hydrogenation catalyst is 1-10wt%, the content of titanium oxide is 1-10wt%, and the content of aluminum oxide is 40-77.9wt%. Calculated as oxides, the content of active components is 20-35wt%.

[0048] According to the present invention, preferably, based on the total mass of the hydrogenation catalyst, the content of lanthanum oxide in the hydrogenation catalyst is 2-6wt%, the content of titanium oxide is 2-6wt%, the content of aluminum oxide is 55-70.5wt%, and the content of active components in terms of oxides is 25-30wt%.

[0049] In the present invention, when the contents of lanthanum oxide, titanium oxide, aluminum oxide and active components meet the above-mentioned limitations, the hydrogenation catalyst has a better dispersion state and a more excellent catalytic performance.

[0050] According to the present invention, at least two of the metals M are selected from at least two of Mo, W, Co and Ni, preferably Mo-Ni, W-Ni, Mo-Co, Mo-Ni-Co, W-Ni-Co or W-Mo-Ni-Co.

[0051] In the present invention, N-graphene and the alumina-lanthanum oxide-titanium oxide composite carrier can further improve the hydrodesulfurization and denitrification performance.

[0052] According to the present invention, the shape of the hydrogenation catalyst is sheet, sphere, cylindrical bar, special-shaped bar, granule or toothed ball.

[0053] According to the present invention, the special-shaped strip is in the shape of a clover, a four-leaf clover or a butterfly.

[0054] According to the present invention, the diameter of the cylindrical bar or the special-shaped bar is 1.0-1.8 mm.

[0055] According to the present invention, the specific surface area of ​​the hydrogenation catalyst is 200-300m 2 / g.

[0056] According to the present invention, the pore volume of the hydrogenation catalyst is 0.4-0.7 mL / g.

[0057] According to the present invention, the lateral pressure strength of the hydrogenation catalyst is 160-200 N / cm.

[0058] According to the present invention, the bulk density of the hydrogenation catalyst is 0.6-0.9 g / cm 3 .

[0059] In the present invention, the hydrogenation catalyst has specific components and contents, so that the hydrogenation catalyst has good lateral pressure strength and specific specific surface area, pore volume and bulk density.

[0060] According to the present invention, the specific surface area of ​​the hydrogenation catalyst is 230-260m 2 / g.

[0061] According to the present invention, the pore volume of the hydrogenation catalyst is 0.45-0.65 mL / g.

[0062] According to the present invention, the lateral pressure strength of the hydrogenation catalyst is 170-190 N / cm.

[0063] According to the present invention, the bulk density of the hydrogenation catalyst is 0.7-0.8 g / cm 3 .

[0064] According to the present invention, the specific surface area of ​​the carrier is 250-500m 2 / g, preferably 280-400m 2 / g.

[0065] According to the present invention, the pore volume of the carrier is 0.6-0.8 mL / g, preferably 0.65-0.75 mL / g.

[0066] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, wherein the preparation method comprises the following steps:

[0067] (1) treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, an extrusion aid, and a binder to obtain a carrier;

[0068] (2) mixing an aqueous solution containing an active component precursor and N-graphene to obtain a dispersion, wherein the active component precursor is a compound of at least two selected from metals M;

[0069] (3) immersing the support in the dispersion, drying, and calcining to obtain a hydrogenation catalyst precursor;

[0070] or:

[0071] A. treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, N-graphene, an extrusion aid, and a binder to obtain a base material;

[0072] B. mixing aqueous solutions containing active component precursors to obtain an impregnation solution, wherein the active component precursors are selected from compounds of at least two of the metals M;

[0073] C. Immersing the base material in an impregnation solution, drying, and calcining to obtain a hydrogenation catalyst precursor;

[0074] wherein the metal M is selected from Group VIII and Group VIB;

[0075] The amount of N-graphene used is such that the content of N-graphene in the prepared hydrogenation catalyst is 0.01-5 wt % based on the total amount of the hydrogenation catalyst;

[0076] The preparation method further comprises sulfiding the hydrogenation catalyst precursor to obtain the hydrogenation catalyst.

[0077] In the present invention, the preparation method can simply and efficiently realize the preparation of the hydrogenation catalyst, and the prepared hydrogenation catalyst has a large number of mesoporous structures and excellent hydrodesulfurization and denitrification performance.

[0078] In the present invention, the N-graphene is not particularly limited and can be prepared according to common preparation methods in the art or a commercial product.

[0079] In the present invention, the support is impregnated with the dispersion in step (2). The dispersion contains an aqueous solution of an active component precursor and N-graphene. Since N-graphene is insoluble and has very small, nanometer-scale, particle size, when added to the aqueous solution of the active component precursor, the N-graphene is stirred and mixed, resulting in a suspension in the aqueous solution. Finally, the mixture forms a dispersion. The impregnation solution in step (B) contains only the active component precursor and water. In this case, the impregnation solution in step (B) is an aqueous solution of the active component precursor.

[0080] According to the present invention, the amounts of the aluminum-containing compound, the lanthanum-containing compound and the titanium-containing compound are such that, based on the total amount of the hydrogenation catalyst, the content of lanthanum oxide in the prepared hydrogenation catalyst is 1-10 wt%, the content of titanium oxide is 1-10 wt%, and the content of aluminum oxide is 40-77.9 wt%.

[0081] In the present invention, the introduction of titanium oxide in the alumina-lanthanum oxide-titania composite carrier improves the hydrodesulfurization and denitrification performance of the hydrogenation catalyst. Specifically, titanium oxide has a variable valence state, which can adjust the surface properties of the carrier, change the distribution and chemical state of the active components, and enhance the hydrogen overflow activity.

[0082] According to the present invention, the amounts of the aluminum-containing compound, the lanthanum-containing compound and the titanium-containing compound are such that, in the prepared hydrogenation catalyst, based on the total amount of the hydrogenation catalyst, the content of lanthanum oxide is 2-6 wt%; the content of titanium oxide is 2-6 wt%; and the content of aluminum oxide is 55-70.5 wt%.

[0083] In the present invention, when the content of lanthanum oxide and titanium oxide is 2-6 wt%, the hydrodesulfurization and denitrification performance of the hydrogenation catalyst is further improved.

[0084] According to the present invention, the amount of N-graphene used is such that the N-graphene content in the prepared hydrogenation catalyst is 0.1-3 wt%, more preferably 0.5-3 wt%, based on the total amount of the hydrogenation catalyst.

[0085] According to the present invention, the active component precursor is used in an amount such that the content of the active component in the prepared hydrogenation catalyst is 20-35 wt%, preferably 25-30 wt%, based on the total amount of the hydrogenation catalyst.

[0086] According to the present invention, based on the total amount of materials fed in step (1) or step A, the amount of the extrusion aid is 1-5wt%, preferably 2-4wt%; the amount of the binder is 1-10wt%, preferably 4-8wt%.

[0087] In the present invention, the total amount of materials fed in step (1) is the total amount of the aluminum-containing compound, the lanthanum-containing compound, the titanium-containing compound, the extrusion aid and the adhesive.

[0088] In the present invention, the total amount of materials fed in step A is the total amount of the aluminum-containing compound, the lanthanum-containing compound, the titanium-containing compound, N-graphene, the extrusion aid and the binder.

[0089] According to the present invention, in step (1) and step A, the treatment includes mixing, shaping, drying and calcining.

[0090] In the present invention, conventional equipment in the art may be used for mixing and molding, such as a kneader or an extruder.

[0091] According to the present invention, in step (1) and step A, the mixing conditions include: temperature of 20-30° C. and time of 0.5-1 h.

[0092] According to the present invention, in step (1) and step A, the drying conditions include: temperature of 90-120° C. and time of 1-4 hours.

[0093] According to the present invention, in step (1) and step A, the calcination conditions include: temperature of 400-550° C. and time of 1-6 hours.

[0094] In the present invention, the active component is loaded on the carrier by an equal volume impregnation method, and an appropriate amount of the active component precursor is added according to the water absorption rate of the carrier.

[0095] According to the present invention, in step (2), the mixing conditions include: temperature of 60-90° C. and time of 1-4 h.

[0096] According to the present invention, in step (3), the immersion conditions include: temperature of 20-60°C, preferably 25-40°C, and time of 0.5-5h, preferably 1-3h.

[0097] According to the present invention, in step (3), the calcination conditions include: a temperature of 400-550° C., preferably 400-500° C., and a time of 2-6 hours, preferably 3-5 hours.

[0098] According to the present invention, in step B, the mixing conditions include: temperature of 60-90° C. and time of 1-4 h.

[0099] According to the present invention, in step C, the immersion conditions include: temperature of 20-60° C., preferably 25-40° C., and time of 0.5-5 h, preferably 1-3 h.

[0100] According to the present invention, in step C, the calcination conditions include: a temperature of 400-550° C., preferably 400-500° C., and a time of 2-6 hours, preferably 3-5 hours.

[0101] According to the present invention, the extrusion aid is selected from at least one of starch, sesbania powder, polyvinyl alcohol, methyl cellulose and polyethylene glycol.

[0102] According to the present invention, the binder is selected from at least one of nitric acid, citric acid, oxalic acid and tartaric acid.

[0103] According to the present invention, the lanthanum-containing compound is selected from at least one of lanthanum-containing organic salts, lanthanum-containing inorganic salts and lanthanum-containing oxides, preferably at least one of lanthanum nitrate, lanthanum acetate, lanthanum oxide, lanthanum carbonate, lanthanum chloride and lanthanum acetylacetonate.

[0104] According to the present invention, the titanium-containing compound is selected from at least one of titanium-containing organic salts, titanium-containing inorganic salts and titanium-containing oxides, preferably at least one of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, titanium dioxide, titanium tetrachloride, titanium trichloride, titanium sulfate and metatitanic acid.

[0105] The aluminum-containing compound is selected from at least one of aluminum-containing organic salts, aluminum-containing inorganic salts and aluminum-containing oxides, and is preferably at least one of pseudo-boehmite, boehmite and gibbsite.

[0106] According to the present invention, the active component precursor is selected from at least two of a cobalt-containing metal compound, a nickel-containing metal compound, a molybdenum-containing metal compound, or a tungsten-containing metal compound.

[0107] According to the present invention, the cobalt-containing metal compound is at least one selected from the group consisting of cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, basic cobalt carbonate, cobalt acetate and cobalt citrate.

[0108] According to the present invention, the nickel-containing metal compound is at least one selected from nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, basic nickel carbonate, nickel acetate and nickel citrate.

[0109] According to the present invention, the molybdenum-containing metal compound is selected from at least one of molybdenum trioxide, molybdic acid, ammonium molybdate, ammonium paramolybdate and phosphomolybdic acid.

[0110] According to the present invention, the tungsten-containing metal compound is selected from at least one of tungsten trioxide, tungstic acid, ammonium metatungstate hydrate, ammonium paratungstate and phosphotungstic acid.

[0111] In the present invention, the sulfurization in the preparation method can cause the hydrogenation catalyst to contain metal M sulfide. The sulfurization can be conventional sulfurization in the art. The sulfurization can be performed directly during the preparation of the hydrogenation catalyst, or it can be performed online after the catalyst is loaded before the actual hydrogenation reaction to take into account the effects of oxidation during storage and transportation of the catalyst.

[0112] The third aspect of the present invention provides a hydrogenation catalyst prepared by the above preparation method.

[0113] A fourth aspect of the present invention provides use of the above hydrogenation catalyst in petroleum refining.

[0114] The present invention will be described in detail below through examples.

[0115] Unless otherwise specified, all reagents used in the present invention are commercially available.

[0116] N-Glydene was purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd. The nitrogen content of N-Glydene was greater than 10 wt % and less than 20 wt %. The structural formula of N-Glydene used in the embodiment of the present invention is similar to that shown in formula (1):

[0117] The surface morphology of the hydrogenation catalyst was characterized by transmission electron microscopy (TEM). The model of the TEM used was JEM-2010, and the test conditions of the TEM were: operating voltage 200 kV.

[0118] The pore structure of the hydrogenation catalyst was examined using the BET test method. Specifically, the ASAP2405M was used. The specific surface area and pore volume of the hydrogenation catalyst and composite support were determined using the Brunauer-Emmett-Taller (BET) method. The mesopore distribution curve was calculated from the desorption curve using the Barrett-Joyner-Halenda (BJH) method.

[0119] The metal oxide content of the hydrogenation catalyst is obtained by calculation.

[0120] The lateral pressure strength of the hydrogenation catalyst was measured by a particle strength testing machine, the instrument model was ZQJ-2.

[0121] Preparation Example - Preparation of composite carrier

[0122] Preparation Example 1

[0123] 100g of pseudo-boehmite, 11.9g of lanthanum nitrate hexahydrate (corresponding to 4.48g of lanthanum oxide), 19.04g of tetrabutyl titanate (corresponding to 4.48g of titanium oxide), 3.8g of sesbania powder, 3.8g of nitric acid, and 3.8g of citric acid were weighed and added to deionized water. The mixture was uniformly mixed and kneaded, and the mixture was extruded into 1.5mm clover-shaped strips. The strips were dried at 100°C for 3h and then calcined at 500°C for 4h to obtain Carrier A1. The extrusion aid was used in an amount of 2.8wt% based on the total amount of materials charged, and the binder was used in an amount of 5.6wt%.

[0124] Preparation Example 2

[0125] 100g of pseudo-boehmite, 14.25g of lanthanum acetate (corresponding to 14.7g of lanthanum oxide), 42g of tetraethyl titanate (corresponding to 14.7g of titanium oxide), 5g of sesbania powder, 5g of nitric acid, and 5g of citric acid were weighed and added to deionized water. The mixture was uniformly mixed and kneaded, and the mixture was extruded into 1.5mm clover-shaped strips. The strips were dried at 90°C for 2h and then calcined at 500°C for 4h to obtain Carrier A2. The extrusion aid was used in an amount of 2.9wt% based on the total amount of materials charged, and the binder was used in an amount of 5.8wt%.

[0126] Preparation Example 3

[0127] 100g of pseudo-boehmite, 0.99g of lanthanum oxide, 0.99g of titanium oxide, 3.3g of sesbania powder, 3.3g of nitric acid, and 3.3g of citric acid were weighed and added to deionized water. The mixture was uniformly mixed and kneaded, and the mixture was extruded into 1.5mm clover-shaped strips. The strips were dried at 120°C for 4 hours and then calcined at 500°C for 4 hours to obtain Carrier A3. The extrusion aid was used in an amount of 2.9wt% based on the total amount of materials charged, and the binder was used in an amount of 5.9wt%.

[0128] Preparation Example 4

[0129] 100g of pseudo-boehmite, 6.3g of lanthanum carbonate (corresponding to 4.48g of lanthanum oxide), 10.64g of titanium tetrachloride (corresponding to 4.48g of titanium oxide), 2.24g of N-graphene, 3.8g of sesbania powder, 3.8g of nitric acid, and 3.8g of citric acid were weighed and added to deionized water. The mixture was uniformly mixed and kneaded, and the mixture was extruded into 1.5mm clover-shaped strips. The strips were dried at 100°C for 3h and then calcined at 500°C for 4h to obtain base material A4. The extrusion aid was used in an amount of 2.9wt% based on the total amount of materials charged, and the binder was used in an amount of 5.8wt%.

[0130] Example - Preparation of Hydrogenation Catalyst

[0131] The amounts of the precursor and the carrier used in the examples are such that the contents of the components of the prepared hydrogenation catalyst are as shown in Table 1.

[0132] Example 1

[0133] The molybdenum oxide precursor and the nickel oxide precursor were dissolved in deionized water, heated to 70° C., N-graphene was added, and stirring was continued to mix uniformly to obtain a dispersion B1.

[0134] Carrier A1 was added to dispersion B1, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C1. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0135] Example 2

[0136] The molybdenum oxide precursor and the cobalt oxide precursor were dissolved in deionized water, heated to 70° C., N-graphene was added, and stirring was continued to mix uniformly to obtain a dispersion B2.

[0137] Carrier A1 was added to dispersion B2, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C2. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0138] Example 3

[0139] The tungsten oxide precursor and the nickel oxide precursor were dissolved in deionized water, heated to 70° C., N-graphene was added, and stirring was continued to mix uniformly to obtain a dispersion B3.

[0140] Carrier A1 was added to dispersion B3, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C3. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0141] Example 4

[0142] The tungsten oxide precursor and the nickel oxide precursor were heated to 70° C. in deionized water, N-graphene was added, and the mixture was stirred and mixed to obtain a dispersion B4.

[0143] Carrier A2 was added to dispersion B4, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C4. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0144] Example 5

[0145] The molybdenum oxide precursor, the nickel oxide precursor and the cobalt oxide precursor were dissolved in deionized water, heated to 70° C., N-graphene was added, and stirring was continued to mix uniformly to obtain a dispersion B5.

[0146] Carrier A3 was added to dispersion B5, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C5. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0147] Example 6

[0148] The molybdenum oxide precursor and the nickel oxide precursor were dissolved in deionized water, heated to 70° C., and mixed uniformly to obtain an impregnation solution B6.

[0149] Base material A4 was added to impregnation solution B6, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C6. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0150] Example 7

[0151] The tungsten oxide precursor and the nickel oxide precursor were dissolved in deionized water, heated to 70° C., and mixed uniformly to obtain an impregnation solution B7.

[0152] Base material A4 was added to impregnation solution B7, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C7. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0153] Example 8

[0154] The molybdenum oxide precursor, the nickel oxide precursor and the cobalt oxide precursor were dissolved in deionized water, heated to 70° C., and mixed uniformly to obtain an impregnation solution B8.

[0155] Base material A4 was added to impregnation solution B8, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce hydrogenation catalyst C8. The content and performance of each component of the hydrogenation catalyst are shown in Table 1.

[0156] Comparative Example 1

[0157] 100 g of pseudo-boehmite, 3.8 g of sesbania powder, 3.8 g of nitric acid and 3.8 g of citric acid were weighed and added to deionized water, mixed evenly, kneaded, and extruded into 1.5 mm clover-shaped strips. After drying, the strips were calcined at 500° C. for 4 h to obtain the carrier DA1.

[0158] Ammonium molybdate and nickel nitrate were dissolved in deionized water, heated to 70° C., and mixed to obtain an impregnation solution DB1.

[0159] The carrier DA1 was added to the impregnation solution DB1, allowed to stand for 3 hours, dried at 110°C for 3 hours, and then calcined at 400°C for 5 hours to produce the hydrogenation catalyst DC1. The content and performance of the hydrogenation catalyst components are shown in Table 1.

[0160] Comparative Example 2

[0161] A hydrogenation catalyst was prepared according to the preparation method of Example 1, except that the dispersion did not contain N-graphene. Hydrogenation catalyst DC2 was obtained. The content of each component of the hydrogenation catalyst and the performance test are shown in Table 1.

[0162] Comparative Example 3

[0163] A hydrogenation catalyst was prepared according to the method of Example 1, except that the N-graphene content was 6% based on the weight of the catalyst. Hydrogenation catalyst DC3 was obtained. The content of each component of the hydrogenation catalyst and the performance test results are shown in Table 1.

[0164] Table 1* *The remainder is alumina.

[0165] The hydrogenation catalysts prepared in the Examples and Comparative Examples were sulfurized before testing. Petroleum products with varying sulfur and nitrogen contents were used as raw materials, and the sulfurized hydrogenation catalysts of the present invention were used to perform catalytic hydrogenation reactions on the petroleum product raw materials. The sulfur content S1, nitrogen content N1, and aromatic content F1 in the raw materials before the hydrogenation reaction were measured by ultraviolet fluorescence, chemiluminescence, and fluorescence indicator methods. The sulfur content S2, nitrogen content N2, and aromatic content F2 in the resulting product after the hydrogenation reaction were measured. The desulfurization rate and denitrogenation rate of the catalytic hydrogenation reaction were calculated, and the desulfurization rate and denitrogenation rate of the reaction were used to evaluate the activity of the hydrogenation catalyst. Here, desulfurization rate (%) = (S1-S2) / S1×100%; denitrogenation rate (%) = (N1-N2) / N1×100%; and aromatic saturation rate (%) = (F1-F2) / F1×100%.

[0166] Test Case A

[0167] A comparative test of catalyst hydrogenation activity was conducted using 8 g of hydrogenation catalyst and coked diesel with a sulfur content of 7800 ppm and a nitrogen content of 1300 ppm as the evaluation raw material. The reaction conditions were a reaction temperature of 340 °C, a hydrogen partial pressure of 6.4 MPa, a hydrogen-to-oil volume ratio of 500:1, and a volume space velocity of 2.0 h -1 The activity evaluation results of the hydrogenation catalyst are shown in Table 2.

[0168] Table 2

[0169] Test Case B

[0170] A comparative test of catalyst hydrogenation activity was conducted using 8 g of hydrogenation catalyst and a jet fuel feedstock with a sulfur content of 6700 ppm, a nitrogen content of 20 ppm, and an aromatics content of 21%. The reaction conditions were a reaction temperature of 340°C, a hydrogen partial pressure of 7.0 MPa, a hydrogen-to-oil volume ratio of 100:1, and a volume space velocity of 1.3 h-1. -1 The activity evaluation results of the hydrogenation catalyst are shown in Table 3.

[0171] Table 3

[0172] Test Case C

[0173] A hydrogenation activity comparison test was conducted using 8 g of hydrogenation catalyst and wax oil (distillation range 225-521°C) with a sulfur content of 900 ppm and a nitrogen content of 726 ppm as the evaluation raw material. The reaction conditions were a reaction temperature of 340°C, a hydrogen partial pressure of 12 MPa, a hydrogen-to-oil volume ratio of 800:1, and a volume space velocity of 1.5 h -1 The activity evaluation results of the catalyst are shown in Table 4.

[0174] Table 4

[0175] It can be seen from the results in Tables 2-4 that Examples 1-6 using the hydrogenation catalyst of the present invention have more excellent hydrodesulfurization and denitrification performance.

[0176] FIG1 is a BET diagram of the hydrogenation catalyst of Example 1. It can be seen that the hydrogenation catalyst has a large number of mesoporous structures, and the pore diameter is concentrated around 10 nm, so that the hydrogenation catalyst provided by the present invention has excellent hydrodesulfurization and denitrification performance.

[0177] FIG2 is a TEM image of the hydrogenation catalyst of Example 1. It can be seen that the catalyst forms an obvious layered stacking structure, so that the hydrogenation catalyst provided by the present invention has higher hydrodesulfurization and hydrodenitrogenation activity.

[0178] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A hydrogenation catalyst, characterized in that The hydrogenation catalyst comprises: a carrier, an active component and N-graphene; wherein the active component is loaded on the carrier, and the N-graphene is loaded on the carrier or mixed in the carrier; Wherein, the carrier comprises an aluminum oxide-lanthanum oxide-titanium oxide composite carrier; Wherein, the active component is selected from sulfides of at least two kinds of metals M; Wherein, the metal M is selected from Group VIII and Group VIB; Wherein, based on the total mass of the hydrogenation catalyst, the content of N-graphene in the hydrogenation catalyst is 0.01-5wt%.

2. The hydrogenation catalyst according to claim 1, wherein Based on the total mass of the hydrogenation catalyst, the content of N-graphene in the hydrogenation catalyst is 0.1-3wt%; Preferably, based on the total mass of the hydrogenation catalyst, the content of lanthanum oxide in the hydrogenation catalyst is 1-10wt%, the content of titanium oxide is 1-10wt%, the content of aluminum oxide is 40-77.9wt%, and the content of active components is 20-35wt% in terms of oxides; Preferably, based on the total mass of the hydrogenation catalyst, the content of lanthanum oxide in the hydrogenation catalyst is 2-6wt%, the content of titanium oxide is 2-6wt%, the content of aluminum oxide is 55-70.5wt%, and the content of active components in terms of oxides is 25-30wt%.

3. The hydrogenation catalyst according to claim 1 or 2, wherein At least two of the metals M are selected from at least two of Mo, W, Co and Ni, preferably Mo-Ni, W-Ni, Mo-Co, Mo-Ni-Co, W-Ni-Co or W-Mo-Ni-Co.

4. The hydrogenation catalyst according to any one of claims 1 to 3, wherein The specific surface area of ​​the hydrogenation catalyst is 200-300m 2 / g; Preferably, the pore volume of the hydrogenation catalyst is 0.4-0.7 mL / g; Preferably, the lateral pressure strength of the hydrogenation catalyst is 160-200 N / cm; Preferably, the bulk density of the hydrogenation catalyst is 0.6-0.9 g / cm 3 .

5. The hydrogenation catalyst according to any one of claims 1 to 4, wherein The specific surface area of ​​the hydrogenation catalyst is 230-260m 2 / g; Preferably, the pore volume of the hydrogenation catalyst is 0.45-0.65 mL / g; Preferably, the lateral pressure strength of the hydrogenation catalyst is 170-190 N / cm; Preferably, the bulk density of the hydrogenation catalyst is 0.7-0.8 g / cm 3 .

6. A method for preparing a hydrogenation catalyst, characterized in that: The preparation method comprises the following steps: (1) treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, an extrusion aid and a binder to obtain a carrier; (2) mixing an aqueous solution containing an active component precursor and N-graphene to obtain an impregnation solution, wherein the active component precursor is selected from compounds of at least two of the metals M; (3) impregnating the support into an impregnation solution, drying, and calcining to obtain a hydrogenation catalyst precursor; or: A. treating an aluminum-containing compound, a lanthanum-containing compound, a titanium-containing compound, N-graphene, an extrusion aid and a binder to obtain a base material; B. mixing aqueous solutions containing active component precursors to obtain an impregnation solution, wherein the active component precursors are selected from compounds of at least two of the metals M; C. Immersing the base material in an impregnation solution, drying, and calcining to obtain a hydrogenation catalyst precursor; Wherein, the metal M is selected from Group VIII and Group VIB; The amount of N-graphene used is such that the content of N-graphene in the prepared hydrogenation catalyst is 0.01-5wt% based on the total amount of the hydrogenation catalyst; Wherein, the preparation method further comprises sulfiding the hydrogenation catalyst precursor to obtain the hydrogenation catalyst.

7. The preparation method according to claim 6, wherein: The aluminum-containing compound, the lanthanum-containing compound and the titanium-containing compound are used in such an amount that, based on the total amount of the hydrogenation catalyst, the content of lanthanum oxide is 1-10 wt %, the content of titanium oxide is 1-10 wt %, and the content of aluminum oxide is 40-77.9 wt %; Preferably, the aluminum-containing compound, the lanthanum-containing compound and the titanium-containing compound are used in an amount such that the obtained In the hydrogenation catalyst, based on the total amount of the hydrogenation catalyst, the content of lanthanum oxide is 2-6wt%; the content of titanium oxide is 2-6wt%; the content of aluminum oxide is 55-70.5wt%; Preferably, the amount of N-graphene used is such that the N-graphene content in the prepared hydrogenation catalyst is 0.1-3 wt % based on the total amount of the hydrogenation catalyst; Preferably, the active component precursor is used in an amount such that the content of the active component in the prepared hydrogenation catalyst is 20-35wt%, preferably 25-30wt%, based on the total amount of the hydrogenation catalyst; Preferably, based on the total amount of materials fed in step (1) or step A, the amount of the extrusion aid is 1-5wt%, preferably 2-4wt%; the amount of the binder is 1-10wt%, preferably 4-8wt%.

8. The preparation method according to claim 6 or 7, wherein: In step (2), the mixing conditions include: temperature of 60-90° C. and time of 1-4 h; Preferably, in step (3), the conditions for the immersion include: a temperature of 20-60°C, preferably 25-40°C, and a time of 0.5-5h, preferably 1-3h; Preferably, in step (3), the calcination conditions include: a temperature of 400-550° C., preferably 400-500° C., and a time of 2-6 h, preferably 3-5 h; Preferably, in step B, the mixing conditions include: temperature of 60-90° C., time of 1-4 h; Preferably, in step C, the immersion conditions include: temperature of 20-60°C, preferably 25-40°C, time of 0.5-5h, preferably 1-3h; Preferably, in step C, the calcination conditions include: temperature of 400-550° C., preferably 400-500° C., and time of 2-6 h, preferably 3-5 h.

9. The preparation method according to claim 6 or 7, wherein: The lanthanum-containing compound is selected from at least one of a lanthanum-containing organic salt, a lanthanum-containing inorganic salt and a lanthanum-containing oxide, and is preferably at least one of lanthanum nitrate, lanthanum acetate, lanthanum oxide, lanthanum carbonate, lanthanum chloride and lanthanum acetylacetonate; Preferably, the titanium-containing compound is selected from at least one of titanium-containing organic salts, titanium-containing inorganic salts and titanium-containing oxides, preferably at least one of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, titanium dioxide, titanium tetrachloride, titanium trichloride, titanium sulfate and metatitanic acid; Preferably, the aluminum-containing compound is selected from at least one of an aluminum-containing organic salt, an aluminum-containing inorganic salt and an aluminum-containing oxide, and is preferably at least one of pseudo-boehmite, boehmite and gibbsite; Preferably, the active component precursor is selected from at least two of a cobalt-containing metal compound, a nickel-containing metal compound, a molybdenum-containing metal compound or a tungsten-containing metal compound; Preferably, the cobalt-containing metal compound is selected from at least one of cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, basic cobalt carbonate, cobalt acetate and cobalt citrate; Preferably, the nickel-containing metal compound is selected from at least one of nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, basic nickel carbonate, nickel acetate and nickel citrate; Preferably, the molybdenum-containing metal compound is selected from at least one of molybdenum trioxide, molybdic acid, ammonium molybdate, ammonium paramolybdate and phosphomolybdic acid; Preferably, the tungsten-containing metal compound is selected from at least one of tungsten trioxide, tungstic acid, ammonium metatungstate hydrate, ammonium paratungstate and phosphotungstic acid.

10. A hydrogenation catalyst prepared by the preparation method according to any one of claims 6 to 9.

11. Use of the hydrogenation catalyst according to any one of claims 1 to 5 and 10 in petroleum refining.

Images