Hydrogenation catalyst, preparation method therefor and use thereof

Abstract

The present invention provides a hydrogenation catalyst, and a preparation method therefor and a use thereof. The catalyst of the present invention comprises an active component and a carrier, wherein the active component is composed of Ni, Mo, and P, and the carrier is a composite oxide comprising magnesium oxide, aluminum oxide, and silicon oxide; and on the basis of the weight of the catalyst, the mass ratio of Ni to Mo in the active component is 1.1-5, preferably 1.9-2.3, and Ni is calculated as NiO and Mo is calculated as MoO3. The active component of the catalyst of the present invention contains a high content of nickel. When used for the second-stage hydrogenation of cracked gasoline, the catalyst can be suitable for treating a raw material having a higher diene content, shows relatively strong monoolefin saturation performance and desulfurization and denitrification activity, can effectively inhibit carbon deposition, and has high stability. Therefore, the catalyst of the present invention is particularly suitable for use in industrial production of the second-stage hydrogenation of cracked gasoline or a fraction thereof.

Description

Hydrogenation catalyst, its preparation method and use TECHNICAL FIELD

[0001] The present invention relates to the field of hydrogenation catalysts, in particular to a hydrogenation catalyst comprising an active component with a high content of nickel, which is particularly suitable for the second-stage hydroprocessing of pyrolysis gasoline or fractions thereof, and to a method for the preparation and use of the catalyst. BACKGROUND

[0002] Ethylene plants produce ethylene from light hydrocarbons, naphtha, diesel or even vacuum gas oil as feedstock in the presence of steam at high temperature. In this process, a liquid by-product containing C5+ hydrocarbons is produced, wherein the liquid by-product having a dry point of up to 205°C is pyrolysis gasoline (also known as pygas). The utilization of pyrolysis gasoline is one of the main ways to improve the overall economic benefit of ethylene plants. Generally, pyrolysis gasoline has a complex composition and poor thermal stability. The utilization of pyrolysis gasoline is carried out by means of second-stage hydroprocessing, wherein dienes and styrene are selectively removed in the first-stage hydroprocessing and olefins and sulfur / nitrogen-containing compounds are further removed in the second-stage hydroprocessing. Currently, the second-stage hydroprocessing of pyrolysis gasoline in industry mainly uses various fractions of pyrolysis gasoline (such as C6-C8 hydrocarbon compound fraction) or pyrolysis gasoline itself as feedstock, wherein the catalyst used in the second-stage hydroprocessing is mainly a Co(Ni)-Mo(W) / Al2O3 series of hydrofining catalyst.

[0003] On the one hand, in recent years, ethylene plants have rapidly expanded capacity, and there are differences in their feedstock and cracking conditions, which result in the variability of pyrolysis gasoline, as one of the by-products of ethylene plants, in composition, heaviness, and sulfur content. On the other hand, the space velocity of the hydrogenation unit is also getting higher and higher. These changes have greatly affected the performance of the first-stage hydroprocessing catalyst, resulting in an increase in the diene content of the product of the first-stage hydroprocessing, which is used as feedstock for the second-stage hydroprocessing. Accordingly, this results in the second-stage hydroprocessing catalyst suffering from poor mono-olefin saturation performance, easy coking, short service life, and the like. Therefore, there is a need to develop a hydrogenation catalyst that can adapt to the working conditions of high diene feedstock, has high mono-olefin saturation performance, desulfurization and denitrification performance at a lower temperature, and has good anti-coking performance and long service life.

[0004] A catalyst for the second-stage hydrofining of pyrolysis gasoline and its preparation method are described in Chinese patent CN1353168A. The preparation method comprises: using an alumina precursor, adding a polymer and a metal of the fourth subgroup during molding, drying in air for 2-14 hours, calcining at 400-700°C to obtain a composite oxide carrier containing a metal of the fourth subgroup, then impregnating with an ammonia co-impregnation solution containing Co, Mo, Ni active components, drying at 100-120°C for 2-14 hours, and calcining in air at 400-700°C for 2.5-8.5 hours to obtain the catalyst. The catalyst has only about 16% of the total pore volume in pores greater than 5 nm, which is not conducive to the diffusion of heavy feedstocks. At the same time, the catalyst has a poor ability to saturate mono-olefins, and has a high hydrogenation reaction start-up temperature and poor stability for high diene feedstocks.

[0005] US4059504 discloses a Ni-W catalyst for the hydrogenation of pyrolysis gasoline. The preparation method comprises: adding tungsten oxide to an aqueous solution of nickel nitrate to prepare an impregnation solution, loading on an alumina carrier, and drying in air and calcining at high temperature for 3 hours to obtain the catalyst. The catalyst has a specific surface area of less than 150 m 2 / g, which results in low activity of the catalyst. In addition, when used to treat pyrolysis gasoline with a high diene content, the catalyst has a short service life.

[0006] A hydrofining catalyst and its preparation method are described in Chinese patent CN102861593A. The catalyst carrier is titanium-modified γ-alumina, and the active components are oxides of molybdenum, cobalt and nickel. With the total weight of the catalyst being 100%, CoO in the active components accounts for 2.0-7.5% of the total weight of the catalyst, MoO3 accounts for 4.0-18.0% of the total weight of the catalyst, NiO accounts for 0.2-5.0% of the total weight of the catalyst, the auxiliary agent accounts for 0.05-1.0% of the total weight of the catalyst, and the balance is the carrier. It is said that the catalyst can hydrogenate and saturate mono-olefins while hydrogenating desulfurizing oil, and can adapt to the process conditions of heavy feedstocks, variable sulfur content and high liquid space velocity faced by the second-stage hydroprocessing of pyrolysis gasoline. However, the catalyst can only adapt to pyrolysis gasoline feedstocks with a low diene content (diene ≤ 2.0 g I2 / 100 g Oil).

[0007] Chinese patent CN101037614 introduces a preparation method and application of a hydrofining catalyst, wherein the catalyst is mainly used for the second-stage hydroprocessing of low distillate oil in pyrolysis gasoline, especially C6-C8distillate oil. The catalyst has Co, Mo and Ni as active components, adds appropriate additives, and γ-alumina as a carrier. Specifically, the catalyst has a weight percentage composition of MoO314-20%, CoO 1-6%, NiO 1-4%, alkali metal additives 1-3%, additives P and the like 1-5%, additives Si and the like 1-3%, and the balance is γ-alumina. The pore volume of the catalyst is 0.45-0.65cm 3 / g, and the specific surface area is 150-280m 2 / g. The catalyst has good hydrogenation effect on light distillate oil such as C6-C8distillate oil, but there is no report on the hydrogenation effect of the catalyst on C6-C9+raw materials. Moreover, it can only adapt to intermediate distillate raw materials with low diene content (diene value ≤2.0gI2 / 100gOil). At the same time, the catalyst preparation process will have a certain impact on the environment.

[0008] Chinese patent CN109317159B introduces a pyrolysis gasoline hydrofining catalyst. The catalyst has molybdenum, cobalt, nickel and strontium as active components, and silicon oxide-alumina as a carrier. Specifically, the catalyst includes 9-19wt% of molybdenum oxide, 3.0-8.5wt% of cobalt oxide, 0.2-3.5wt% of nickel oxide, 0.1-2.0wt% of strontium oxide, and 75-85wt% of the silicon oxide-alumina carrier, based on the total weight of the catalyst, wherein the carrier has uneven distribution of micropores, mesopores and macropores. The catalyst has good gum resistance, strong resistance to arsenic, sulfur and water. However, the catalyst can only adapt to full-range raw materials with low diene content (diene value ≤1.5gI2 / 100g Oil).

[0009] Therefore, although various second-stage hydroprocessing catalysts for the second-stage hydroprocessing of pyrolysis gasoline have been successfully developed in the prior art, they have poor tolerance to high content of dienes in the second-stage hydroprocessing raw materials, and thus still suffer from various problems such as poor mono-olefin saturation performance and desulfurization and denitrification performance, easy coking, short service life, etc. SUMMARY

[0010] The present application aims at solving the problems of the prior art two-stage hydrogenation catalyst, such as poor tolerance to high content of diene in raw material, poor hydrogenation performance, easy coking, short service life, etc. To this end, the present application provides a hydrogenation catalyst, a preparation method and application thereof. The active component of the hydrogenation catalyst of the present application contains high content of nickel. When the catalyst is used for two-stage hydrogenation treatment of pyrolysis gasoline, it can be applied to treat raw material with higher content of diene, and exhibits strong mono-olefin saturation performance, desulfurization and denitrification activity, and can effectively inhibit carbon deposition and has high stability. Therefore, the catalyst of the present application is particularly suitable for industrial production of two-stage hydrogenation treatment of pyrolysis gasoline or its fractions.

[0011] In one aspect, the present application provides a hydrogenation catalyst, which comprises an active component and a carrier, wherein the active component is composed of Ni, Mo and P, and the carrier is a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide; the mass ratio of Ni and Mo in the active component is 1.1-5, preferably 1.9-2.3, based on the weight of the catalyst, wherein Ni is calculated as NiO and Mo is calculated as MoO3.

[0012] In another aspect, the present application provides a preparation method of the hydrogenation catalyst, which comprises the following steps:

[0013] (A) providing a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide;

[0014] (B) preparing an impregnation solution with a Ni source, a Mo source and a P source, impregnating the above composite oxide in the impregnation solution, and performing first drying and first calcination on the impregnated composite oxide to obtain the hydrogenation catalyst.

[0015] In another aspect, the present application provides the use of the hydrogenation catalyst in the hydrofining of petroleum hydrocarbons, preferably in the two-stage hydrogenation treatment of pyrolysis gasoline or its fractions.

[0016] Specifically, the present application relates to the following aspects:

[0017] 1. A hydrogenation catalyst, wherein the active component of the catalyst is composed of Ni, Mo and P, and the carrier is a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide; the mass ratio of Ni and Mo in the active component is 1.1-4.8, based on the weight of the catalyst.

[0018] 2. The catalyst of any one of the preceding aspects, wherein the content of the active component in the catalyst, calculated as oxides, is as follows: the content of NiO is 10.0-20.0%, the content of MoO3 is 5.0-10.0%, and the content of P2O5 is 1.0-5.0%, based on the weight of the catalyst; preferably, the content of NiO is 10.0-15.0%, the content of MoO3 is 7.0-8.0%, and the content of P2O5 is 2.0-5.0%.

[0019] 3. The catalyst according to any one of the preceding aspects, wherein the composite oxide support comprises, based on the weight of the composite oxide support, 90.0 to 98.0% of alumina, 1.0 to 5.0% of silica, and 1.0 to 5.0% of magnesia; preferably 91.0 to 93.0% of alumina, 4.7 to 5.0% of silica, and 2.5 to 3.7% of magnesia.

[0020] 4. The catalyst according to any one of the preceding aspects, wherein the catalyst has a specific surface area of 150 to 250 m2 / g and a total pore volume of 0.4 to 0.6 ml / g; preferably a specific surface area of 180 to 249 m2 / g and a total pore volume of 0.5 to 0.59 ml / g. 2 2

[0021] 5. The catalyst according to any one of the preceding aspects, wherein the catalyst has 60 to 80 area% of acid sites corresponding to 150 to 250°C and 20 to 40 area% of acid sites corresponding to 250 to 450°C; preferably 65 to 75 area% of acid sites corresponding to 150 to 250°C and 22 to 26 area% of acid sites corresponding to 250 to 450°C.

[0022] 6. A method for producing a hydrogenation catalyst, comprising the steps of:

[0023] (1) dissolving a magnesium source in water together with at least one of citric acid, nitric acid, and acetic acid to prepare a solution A;

[0024] (2) mixing an aluminum source and a silicon source, adding the solution A to the mixture, and extruding the mixture to form a shape, and then drying the shape at 100 to 130°C for 12 to 24 hours and calcining the shape at 500 to 800°C for 4 to 8 hours to produce a composite oxide support;

[0025] (3) impregnating the composite oxide support with a solution containing a nickel source, a molybdenum source, and a phosphorus source, standing the support for 4 to 8 hours, and then drying the support at 100 to 130°C for 2 to 4 hours and calcining the support at 400 to 600°C for 4 to 8 hours to produce a hydrogenation catalyst.

[0026] 7. The method according to any one of the preceding aspects, wherein the magnesium source is at least one of magnesium nitrate and magnesium acetate; the silicon source is at least one of silica and silica sol; the aluminum source is preferably pseudoboehmite; and the concentration of the solution A is preferably 0.27 to 0.52 mol / L.

[0027] ​​8. The method of any of the preceding aspects, wherein the Ni source is at least one of nickel nitrate, nickel acetate or nickel carbonate; the Mo source is at least one of ammonium molybdate or molybdenum oxide; the P source is at least one of phosphoric acid or phytic acid; the solution of step (3) further comprises citric acid; and the concentration of the Ni, Mo, P-containing solution is preferably 2.6-4.2 mol / L.

[0028] 9. Use of the hydrogenation catalyst of any of the preceding aspects in the hydrofining of petroleum hydrocarbons, preferably in the second-stage hydroprocessing of steam-cracked or catalytically cracked gasoline which is heavy and poor in quality.

[0029] 10. Use of the hydrogenation catalyst of any of the preceding aspects in the second-stage hydroprocessing of C6-C8, C6-C9+ and C5-C9 fractions of cracked gasoline, preferably the diene value of the fraction is 3-8 g I2 / 100 g.

[0030] Preferably, the reaction conditions of the second-stage hydroprocessing include: using an adiabatic bed reactor, the reaction pressure is not less than 2.7 MPa, the inlet temperature is 220-230°C, the space velocity of fresh feed oil is 2.0-3.0 h - 1 , and the hydrogen / oil volume ratio is 400-1000.

[0031] 11. The use of any of the preceding aspects, wherein the catalyst is pre-sulfided before being used for hydrogenation.

[0032] The pre-sulfiding includes the steps of: inputting hydrogen at a pressure of 2.6-3.0 MPa, the hydrogen volume space velocity is 200-400 h -1 ,

[0033] Raising the temperature of the catalyst bed to 160-180°C, starting to input the sulfidation oil, the sulfidation oil volume space velocity is 3.0-5.0 h -1 ,

[0034] Continuing to raise the temperature of the catalyst bed to 290-320°C at a rate of 30-50°C / h, maintaining for 20-40 hours, lowering the temperature to 220-230°C, stopping the input of the sulfidation oil to perform pre-sulfiding.

[0035] The sulfidation oil is preferably a mixed solution of cyclohexane and dimethyl disulfide, wherein the sulfur content is 1000-4000 ppm.

[0036] Compared with the catalysts of the prior art, the catalysts of the present application have the following advantages:

[0037] The catalyst of the present invention has a support comprising a composite oxide of magnesium oxide, aluminium oxide and silicon oxide. By introducing magnesium and silicon, the amount of strong and weak acid sites on the surface of the catalyst is adjusted. Generally, the more strong acid sites on the surface of the catalyst, the more likely the catalyst is to coke. The catalyst of the present invention has a lower amount of strong acid sites, thereby delaying the tendency of the catalyst to deactivate due to coking.

[0038] At the same time, the catalyst of the present invention has an active component comprising a relatively high amount of Ni and a relatively low amount of Mo, i.e. the mass ratio (based on oxides) of Ni to Mo in the catalyst is at least 1.1 or higher. The relatively high amount of Ni provides more active sites for the hydrogenation reactions of the hydrocarbons, thereby not only ensuring the saturation of mono-olefins, but also enabling the sufficient hydrogenation of di-olefins. An increase in the amount of di-olefins in the feedstock means an increase in the amount of components that are prone to polymerization, which in turn means that coking is more likely to occur. The catalyst of the present invention is able to effectively hydrogenate mono-olefins and di-olefins, thereby reducing the probability of coking and reducing the coverage of the active sites by coking.

[0039] The magnesium and aluminium in the support have different reactivity with the nickel in the active component. The introduction of magnesium in the support can improve the acid site distribution on the surface of the support and can also hinder the reaction of nickel in the active component with aluminium oxide to form products that are detrimental to the hydrogenation catalysis. Too much or too little silicon and magnesium added to the support can cause the loss of nickel in the active component or the aggregation of the particles, and thus the amount of magnesium and silicon in the support will affect the composition of the active component in the catalyst finally obtained, and thereby the performance of the catalyst. In a preferred embodiment, the amount of silicon oxide and magnesium oxide in the support of the catalyst is selected to match the active component comprising a relatively high amount of Ni and a relatively low amount of Mo, which unexpectedly leads to a further improvement in the performance of the catalyst.

[0040] Thus, the catalyst of the present invention has improved hydrogenation activity, improved resistance to coking, and improved tolerance to feedstocks with a high di-olefin content. In addition, the catalyst of the present invention has a lower start-up temperature.

[0041] Thus, the catalyst of the present invention is suitable for use in the second-stage hydroprocessing of pyrolysis gasoline (e.g. steam pyrolysis gasoline and catalytic pyrolysis gasoline) or a fraction thereof (e.g. a C5-C9 fraction, a C6-C8 fraction or a C6-C9 fraction of pyrolysis gasoline), preferably said pyrolysis gasoline or fraction thereof has a di-olefin content of 3-10 g I2 / 100 g, preferably 5-8 g I2 / 100 g; and optionally a gum content of 40-70 mg / 100 ml. DETAILED DESCRIPTION

[0042] The present application will be described in further detail by the specific embodiments below. It is to be understood that the specific embodiments described herein are merely illustrative and explanatory in nature and are not intended to limit the present application in any manner.

[0043] Any specific numerical values (including numerical values of endpoints) disclosed herein are not intended to be exact, but rather are intended to serve as an approximation. And, unless otherwise indicated, the numerical values are in no way limiting. For example, a numerical value recited as "1.2" is intended to mean "about 1.2," and a numerical value recited as "1.2" is also intended to mean "1.2 + / - 0.1" or "1.2 + / - 0.01", or any other value within a range of 1.0 to 1.4. And, any numerical range recited herein is intended to include all derivatives sub-ranges falling within the range. For example, a range of "1.0 to 1.4" is intended to include every possible subrange between (and including) the minimum and maximum limits of the range. And, any reference to a numerical value is intended to include a range of that value, unless otherwise indicated.

[0044] Unless otherwise indicated, the terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. If a term is defined in this document, and that definition is different from the meaning commonly understood by one of ordinary skill in the art, then the definition provided herein controls over any discordant definition of the term.

[0045] In one aspect, the present application provides a hydrogenation catalyst comprising an active component and a support, wherein the active component consists of Ni, Mo and P, and the support is a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide; the mass ratio of Ni and Mo in the active component is 1.1-5, preferably 1.9-2.3, based on the total weight of the hydrogenation catalyst, Ni is calculated as NiO and Mo is calculated as MoO3.

[0046] The hydrogenation catalyst can be used for the second stage hydrogenation of pyrolysis gasoline or various fractions thereof. Thus, the hydrogenation catalyst is also referred to as "a catalyst for the second stage hydrogenation of a two-stage hydrogenation of pyrolysis gasoline". Generally, the two-stage hydrogenation of pyrolysis gasoline or fractions thereof comprises a first stage hydrogenation and a second stage hydrogenation, wherein the first stage hydrogenation is carried out at a lower temperature in the presence of a first hydrogenation catalyst to convert dienes and styrene in the feedstock oil, and the second stage hydrogenation is carried out at a higher temperature in the presence of a second hydrogenation catalyst to saturate mono-olefins in the feedstock oil and remove nitrogen / sulfur-containing compounds therein.

[0047] In one embodiment, the hydrogenation catalyst comprises, as active components, 10.0-20.0% of Ni, calculated as NiO; 5.0-10.0% of Mo, calculated as MoO3; and 1.0-5.0% of P, calculated as P2O5, based on the total weight of the hydrogenation catalyst; preferably 12.0-18.0% of Ni, calculated as NiO; 5.2-7.8% of Mo, calculated as MoO3; and 2.0-5.0% of P, calculated as P2O5.

[0048] In one embodiment, the composite oxide comprises, based on the weight of the composite oxide: 90.0-98.0% of alumina, 1.0-5.0% of silica and 1.0-5.0% of magnesia; preferably 91.0-93.0% of alumina, 4.7-5.0% of silica and 2.3-3.7% of magnesia.

[0049] In one embodiment, the hydrogenation catalyst has a (BET) specific surface area of 150-250 m2 / g, a total pore volume of 0.4-0.6 ml / g; preferably a (BET) specific surface area of 180-249 m2 / g, a total pore volume of 0.5-0.59 ml / g. 2 2 In one embodiment, the hydrogenation catalyst has a (BET) specific surface area of 150-250 m2 / g, a total pore volume of 0.4-0.6 ml / g; preferably a (BET) specific surface area of 180-249 m2 / g, a total pore volume of 0.5-0.59 ml / g.

[0050] In one embodiment, the hydrogenation catalyst has a (BET) specific surface area of 150-250 m2 / g, a total pore volume of 0.4-0.6 ml / g; preferably a (BET) specific surface area of 180-249 m2 / g, a total pore volume of 0.5-0.59 ml / g.

[0051] ​The catalyst surface has active sites (i.e. acid sites) that provide protons or accept electron pairs. Generally, the amount of different acid sites of a hydrogenation catalyst can be characterized by obtaining the ammonia temperature programmed desorption (NH3-TPD) profile of the catalyst. In the present application, the percentage of the desorption peak area of an acid site to the total desorption peak area in the NH3-TPD profile of the hydrogenation catalyst is used to characterize the amount of each acid site in the hydrogenation catalyst. Specifically, the NH3-TPD profile of the catalyst is obtained by ammonia temperature programmed desorption test. In the present application, the acid sites corresponding to the desorption peak temperature of 150-250°C in the NH3-TPD profile of the catalyst are weak acid, and the acid sites corresponding to the desorption peak temperature of 250-450°C are strong acid. Then the amount of different strength acid sites of the catalyst is shown by fitting the area of the desorption peak of the strong acid and weak acid sites, and calculating the proportion of the desorption peak area of the strong acid and weak acid sites to the total desorption peak area. The amount of different acid sites is one of the important parameters for evaluating the surface properties of the catalyst. The catalyst of the present application has a relatively large amount of weak acid sites and a relatively small amount of strong acid sites, and therefore the catalyst of the present application has improved carbon deposition resistance.

[0052] In another aspect, the present application provides a method for preparing the hydrogenation catalyst, comprising the following steps:

[0053] (A) providing a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide;

[0054] (B) preparing an impregnation solution with a Ni source, a Mo source and a P source, impregnating the above composite oxide in the impregnation solution, and performing first drying and first calcination on the impregnated composite oxide to obtain the hydrogenation catalyst.

[0055] In one embodiment, the step (A) of providing a composite oxide comprises the following steps:

[0056] (1) mixing a magnesium source, water and at least one acid selected from citric acid, nitric acid and acetic acid to obtain a solution A; and

[0057] (2) mixing an aluminum source, a silicon source, an organic additive and the solution A, shaping the mixture, second drying and second calcination to obtain the composite oxide.

[0058] In one embodiment, the magnesium source is selected from at least one of magnesium sulfate, magnesium chloride, magnesium nitrate and magnesium acetate. In one variant, the magnesium ion concentration of the solution A is 0.1-1 mol / L, preferably 0.27-0.52 mol / L. The at least one acid is used in a molar ratio of the at least one acid to magnesium ion of 1:1-1:10.

[0059] In one embodiment, the silicon source is at least one selected from the group consisting of silicon oxide and silica sol; the aluminum source is at least one selected from the group consisting of Pseudoboemite, Boehmite, Gibbsite and Bayerite, preferably Pseudoboemite; and the organic additive is at least one selected from the group consisting of sesbania gum, carboxymethyl cellulose, polyvinyl alcohol and starch, preferably sesbania gum.

[0060] The shaping method is not particularly limited in the present application, and a conventional method in the art can be used. For example, the shaping is extrusion molding. In the present application, the mixture can be shaped into various shapes, which can be various shapes conventionally used in the art. The shape can be regular or irregular, and is preferably regular. For example, a spherical shape, a bar shape, a ring shape, a honeycomb shape or a butterfly shape can be used. The bar shape in the present application can be a cylindrical bar, an elliptical bar (equivalent to a double-leaf bar), or a multi-leaf bar. The present application does not limit the outer shape, length and distribution of the bar shape.

[0061] In step (2), the second drying is performed at 50-200°C for 6-36h, preferably at 100-130°C for 12-24h. The second calcination is performed at 400-1000°C for 2-12h, preferably at 500-800°C for 4-8h. In one variant, the second drying and the second calcination can be performed in an inert atmosphere. The inert atmosphere refers to a gas that is inactive under drying or calcination conditions, for example, nitrogen and a group zero element gas (such as argon).

[0062] In one embodiment, in step (B), the Ni source is at least one selected from the group consisting of nickel nitrate, nickel acetate and nickel carbonate; the Mo source is at least one selected from the group consisting of ammonium molybdate and molybdenum oxide; and the P source is at least one selected from the group consisting of phosphoric acid and phytic acid.

[0063] In one embodiment, the Ni source, the Mo source and the P source are added to deionized water to form the impregnation solution. The amounts of the Ni source, the Mo source and the P source are such that the total concentration of Ni, Mo and P in the impregnation solution is 1-5 mol / L, preferably 2.6-4.2 mol / L, based on elements. In one variant, the impregnation solution further comprises citric acid. Preferably, the amount of citric acid is 0.01-0.1 mol / L, preferably 0.05-0.09 mol / L.

[0064] In step (B), the impregnation is carried out by an equivalent impregnation method. In the present application, the "equivalent impregnation" means that the amount of the impregnation solution is equal to or substantially equal to the saturated adsorption amount of the composite oxide. In one variant, the impregnation in step (B) comprises the steps of: i) measuring the saturated water adsorption rate of the composite oxide of step (A); ii) impregnating the composite oxide in the impregnation solution, wherein the amount of the impregnation solution = the amount of the composite oxide * the saturated water adsorption rate / the density of water. In one variant, the saturated water adsorption rate of the composite oxide is measured as follows: 100 g of the composite oxide of step (A) is soaked in deionized water for 1 hour, drained and wiped off the free water on the surface to obtain the weight of the composite oxide after water absorption. The saturated water adsorption rate is calculated from the weight difference before and after water absorption of the composite oxide, wherein the saturated water adsorption rate (%) = (the weight of the composite oxide after water absorption - 100). The equivalent impregnation allows the impregnation solution to be completely adsorbed by the composite oxide, saving the amount of active components.

[0065] In step (B), the first drying is carried out at 50-150 °C for 1-6 h, preferably at 100-130 °C for 2-4 h. The first calcination is carried out at 400-800 °C for 2-12 h, preferably at 400-600 °C for 4-8 h. In one variant, the first drying and the first calcination can be carried out in an inert atmosphere. The inert atmosphere means a gas that is inactive under the drying or calcination conditions, for example, nitrogen and group zero element gas (such as argon).

[0066] In another aspect, the present application provides the use of the hydrogenation catalyst in the hydrofining of petroleum hydrocarbons, preferably in the secondary hydroprocessing of steam cracking gasoline or a fraction thereof. In one variant, the steam cracking gasoline includes steam cracking gasoline or thermal cracking gasoline. The fraction of the steam cracking gasoline includes, for example, C6-C8 fraction, C6-C9+ fraction or C5-C9 fraction, etc. Preferably, the diene value of the steam cracking gasoline or the fraction thereof is 3-10, preferably 5-8 g I2 / 100 g.

[0067] In one embodiment, the reaction conditions of the secondary hydroprocessing include: using an adiabatic bed reactor, the reaction pressure is not less than 2.7 MPa, the inlet temperature is 220-230 °C, the fresh feed oil space velocity is 2.0-3.0 h -1 , and the hydrogen / oil volume ratio is 400-1000.

[0068] In one embodiment, the catalyst is pre-sulfided before the secondary hydroprocessing is carried out.

[0069] In one variant, the pre-sulfiding comprises the steps of:

[0070] hydrogen is inputted at a pressure of 2.6-3.0 MPa, and the volume space velocity of the hydrogen is 200-400 h -1 ,

[0071] The catalyst bed is heated to 160-180℃, and the sulfuration oil is inputted at a volume space velocity of 3.0-5.0 h -1 ,

[0072] The catalyst bed is continuously heated at a rate of 30-50℃ / h to 290-320℃, maintained at this temperature for 20-40 hours, cooled to 220-230℃, and the input of the sulfuration oil is stopped,

[0073] The sulfuration oil is a mixed solution of cyclohexane and dimethyl disulfide, and the sulfur content is 1000-4000 ppm.

[0074] Examples

[0075] The present application will be described in detail by examples below. The examples are intended to describe but not limit the present application in any way.

[0076] Test methods

[0077] The diene value of the raw material: determined according to UOP326-2008 “Determination of Diene Value by Maleic Anhydride Addition Reaction”, in gI2 / 100g (i.e. gI2 / 100g of raw material);

[0078] The bromine value of the raw material and the product: determined according to SH / T 0630-1996 “Determination of Bromine Value and Bromine Index of Petroleum Products (Coulometric Method)”;

[0079] The sulfur content of the raw material and the product: determined according to SH / T 0689-2000 “Determination of Total Sulfur Content in Light Hydrocarbons, Motor Fuels and Other Oil Products”;

[0080] The nitrogen content of the raw material and the product: determined according to ASTM D4629-17 “Standard Test Method for Determination of Total Nitrogen in Light Petroleum Distillates, Finished Gasoline, and Other Hydrocarbon Oils by Injector / Inlet Oxidative Combustion and Chemiluminescence Detection”;

[0081] The gum content of the raw material: determined according to GB / T 509-1988 “Determination of Actual Gum in Motor Fuels”;

[0082] Amount of acidic sites of the catalyst: measured by NH3-TPD method on an AutoChem III 2930 of Micromeritics Instrument Co. Specifically, 0.15 g of the catalyst sample was placed in a reaction tube with an inner diameter of 4 mm, helium gas was used as the carrier gas (flow rate 30 mL / min), the temperature was raised to 600°C, and after 1 h of constant temperature, it was lowered to 50°C, and ammonia was absorbed for 0.5 h, and after 1.5 h of helium gas purging, the temperature was raised to 600°C at a rate of 10°C / min. The NH3-TPD curve of the catalyst sample was measured, and the peak fitting was performed by PEAKFIT, and the areas of the desorption peaks corresponding to the acidic sites at temperatures of 150-250°C and the acidic sites at temperatures of 250-450°C and the percentages of the areas in the total area of the desorption peaks were calculated.

[0083] Specific surface area and pore volume of the catalyst: measured by low-temperature N2 physical adsorption-desorption (BET) method using TriStar 3000 and ASAP 2020M of Micromeritics Instrument Co. of the United States. Specifically, the catalyst sample was dried at 100°C for 1-2 hours, vacuum degassed at 300°C for 4 hours, and the adsorption-desorption isotherm of the catalyst sample was determined at a temperature of -196°C using N2 as the adsorbate. The specific surface area of the catalyst sample was calculated by the BET equation, and the pore size distribution and pore volume were calculated using the desorption isotherm by the BJH method.

[0084] In the above test, the sample was tested three times, and the average value of the results was taken as the test data.

[0085] Preparation Example

[0086] Example 1

[0087] Pseudo-boehmite 200 g, sesbania powder 4.0 g, and silica sol (SiO2 content 40%) 12 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, and magnesium nitrate 9.5 g were added to water to make a 205 ml solution. The solution was added to the kneader, and the mixture was continuously mixed for 40 minutes, and then the mixture was extruded into wet strips of 1 mm in diameter and 3-leaf clover shape. The wet strips were dried at 100°C for 15 hours and then calcined at 550°C for 6 hours to obtain a support Z1. Example 2

[0088] Ammonium molybdate 21.94 g, nickel nitrate 39.39 g, phosphoric acid 3.24 g, and citric acid 15 g were added to water to make an impregnation solution of 107.4 ml. 100 g of the support Z1 was impregnated with the impregnation solution in equal amounts. The impregnated support was dried at 100°C for 2 hours and calcined at 400°C for 4 hours to obtain a catalyst C1. The composition of the catalyst C1 is shown in Table 1, in which the contents of magnesium oxide and silicon oxide are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide, and phosphorus pentoxide are based on the weight of the catalyst.

[0089] Example 2

[0090] Pseudo-boehmite 200 g, Pannisetum 4.0 g, silica 1.5 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 15.7 g were dissolved in water to make up a solution of 205 ml. The solution was added to the kneader and kneading was continued for 40 minutes, then the wet strip was extruded into 1 mm clover-shaped wet strips. The wet strips were dried at 120°C for 12 hours and then calcined at 800°C for 4 hours to obtain the support Z2.

[0091] Ammonium molybdate 9.21 g, nickel acetate 63.99 g, phytic acid 6.28 g, citric acid 15 g were dissolved in water to make up an impregnation solution of 108.1 ml. 100 g of support Z2 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 130°C for 4 hours and calcined at 600°C for 8 hours to obtain the catalyst C2. The composition of catalyst C2 is shown in Table 1, in which the contents of magnesium oxide and silica are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0092] Example 3

[0093] Pseudo-boehmite 200 g, Pannisetum 4.0 g, silica 3.6 g, silica sol (SiO2 content 40%) 10 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium nitrate 5.0 g, magnesium acetate 10 g were dissolved in water to make up a solution of 205 ml. The solution was added to the kneader and kneading was continued for 40 minutes, then the wet strip was extruded into 1 mm clover-shaped wet strips. The wet strips were dried at 130°C for 24 hours and then calcined at 700°C for 5 hours to obtain the support Z3.

[0094] Molybdenum trioxide 11.11 g, nickel carbonate 33.1 g, phosphoric acid 4.79 g, citric acid 15 g were dissolved in water to make up an impregnation solution of 111.1 ml. 100 g of support Z3 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 120°C for 3 hours and calcined at 500°C for 6 hours to obtain the catalyst C3. The composition of catalyst C3 is shown in Table 1, in which the contents of magnesium oxide and silica are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0095] Example 4

[0096] ​​Pseudo-boehmite 200 g, Pemmen 4.0 g, silica 4.0 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium nitrate 25.0 g were dissolved in water to make up 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the kneaded mass was extruded into 1 mm three-leaf clover shaped wet strips. The wet strips were dried at 110°C for 20 hours and calcined at 600°C for 8 hours to obtain the support Z4. Pseudo-boehmite 200 g, Pemmen 4.0 g, silica 4.0 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium nitrate 25.0 g were dissolved in water to make up 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the kneaded mass was extruded into 1 mm three-leaf clover shaped wet strips. The wet strips were dried at 110°C for 20 hours and calcined at 600°C for 8 hours to obtain the support Z4.

[0097] A mixture of 7.16 g ammonium molybdate and 5.26 g molybdenum oxide, a mixture of 18.69 g nickel acetate and 12.55 g nickel carbonate, a mixture of 1.82 g phosphoric acid and 12.24 g phytic acid, 15 g citric acid were dissolved in water to make up 105.3 ml impregnation solution. 100 g of the support Z4 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 125°C for 3 hours and calcined at 450°C for 7 hours to obtain the catalyst C4. The composition of the catalyst C4 is given in Table 1, where the contents of magnesium oxide and silica are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0098] Example 5

[0099] Pseudo-boehmite 200 g, Pemmen 4.0 g, silica sol (SiO2 content 40%) 18 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 8.0 g were dissolved in water to make up 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the kneaded mass was extruded into 1 mm three-leaf clover shaped wet strips. The wet strips were dried at 120°C for 18 hours and calcined at 550°C for 7 hours to obtain the support Z5. Pseudo-boehmite 200 g, Pemmen 4.0 g, silica sol (SiO2 content 40%) 18 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 8.0 g were dissolved in water to make up 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the kneaded mass was extruded into 1 mm three-leaf clover shaped wet strips. The wet strips were dried at 120°C for 18 hours and calcined at 550°C for 7 hours to obtain the support Z5.

[0100] A mixture of 7.16 g ammonium molybdate and 5.26 g molybdenum oxide, a mixture of 18.69 g nickel acetate and 12.55 g nickel carbonate, a mixture of 1.82 g phosphoric acid and 12.24 g phytic acid, 15 g citric acid were dissolved in water to make up 105.3 ml impregnation solution. 100 g of the support Z4 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 125°C for 3 hours and calcined at 450°C for 7 hours to obtain the catalyst C4. The composition of the catalyst C4 is given in Table 1, where the contents of magnesium oxide and silica are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0101] Example 6

[0102] 9.21g of molybdenum oxide, 29.28g of nickel carbonate, 5.45g of phosphoric acid, and 15g of citric acid were added to water to prepare 105.3ml of impregnation solution. An equal amount of 100g of carrier Z3 was impregnated in this solution. The impregnated carrier was dried at 120°C for 4 hours and calcined at 480°C for 4 hours to produce Catalyst C6. The composition of Catalyst C6 is shown in Table 2, where the contents of magnesium oxide and silicon oxide are based on the weight of the carrier; the contents of nickel oxide, molybdenum trioxide, and phosphorus pentoxide are based on the weight of the catalyst.

[0103] [Example 7]

[0104] 13.95g of ammonium molybdate, 52.63g of nickel nitrate, 3.71g of phosphoric acid, and 15g of citric acid were added to water to prepare 107.6ml of impregnation solution. An equal amount of 100g of carrier Z3 was impregnated in this solution. The impregnated carrier was dried at 125°C for 4 hours and calcined at 550°C for 5 hours to produce catalyst C7. The composition of catalyst C7 is shown in Table 2, where the contents of magnesium oxide and silicon oxide are based on the weight of the carrier; the contents of nickel oxide, molybdenum trioxide, and phosphorus pentoxide are based on the weight of the catalyst.

[0105] [Example 8]

[0106] 2.99g of ammonium molybdate, 5.48g of molybdenum oxide, 12.95g of nickel nitrate, 12.53g of nickel acetate, 11.22g of nickel carbonate, 3.53g of phosphoric acid, and 15g of citric acid were added to water to prepare 102.3ml of impregnation solution. An equal amount of 100g of support Z3 was impregnated in this solution. The impregnated support was dried at 125°C for 4 hours and calcined at 550°C for 5 hours to produce Catalyst C8. The composition of Catalyst C8 is shown in Table 2, where the contents of magnesium oxide and silicon oxide are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide, and phosphorus pentoxide are based on the weight of the catalyst.

[0107] [Example 9]

[0108] Example 5 was repeated except that support Z5 was substituted for support Z1 to obtain catalyst C9. The composition of catalyst C9 is shown in Table 3, where the contents of magnesium oxide and silicon oxide are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide, and phosphorus pentoxide are based on the weight of the catalyst.

[0109] [Example 10]

[0110] Example 5 was repeated except that support Z5 was replaced by support Z5-1 prepared as follows to obtain catalyst C10.

[0111] Pseudo-boehmite 200 g, Pannisetum 4.0 g, silica sol (Si02 content 40%) 18 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 4.0 g were dissolved in water to make a 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the wet strip was extruded into 1 mm three-leaf clover shape. The wet strip was dried at 120°C for 18 hours and then calcined at 550°C for 7 hours to obtain the support Z5-1. The composition of catalyst C10 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide, phosphorus pentoxide is given by weight of the catalyst.

[0112] The composition of catalyst C10 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide, phosphorus pentoxide is given by weight of the catalyst.

[0113] Example 11

[0114] Example 5 was repeated, except that the support Z5 was replaced by support Z5-2 prepared as follows, to obtain catalyst C11.

[0115] Pseudo-boehmite 200 g, Pannisetum 4.0 g, silica sol (Si02 content 40%) 18 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 4.0 g were dissolved in water to make a 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the wet strip was extruded into 1 mm three-leaf clover shape. The wet strip was dried at 120°C for 18 hours and then calcined at 550°C for 7 hours to obtain the support Z5-1. The composition of catalyst C10 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide, phosphorus pentoxide is given by weight of the catalyst.

[0116] The composition of catalyst C10 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide, phosphorus pentoxide is given by weight of the catalyst.

[0117] Example 12

[0118] Example 5 was repeated, except that the support Z5 was replaced by support Z5-3 prepared as follows, to obtain catalyst C11.

[0119] Pseudo-boehmite 200 g, Pannisetum 4.0 g, silica sol (Si02 content 40%) 18 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium acetate 4.0 g were dissolved in water to make a 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the wet strip was extruded into 1 mm three-leaf clover shape. The wet strip was dried at 120°C for 18 hours and then calcined at 550°C for 7 hours to obtain the support Z5-1. The composition of catalyst C10 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide, phosphorus pentoxide is given by weight of the catalyst.

[0120] The composition of catalyst C12 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide and phosphorus pentoxide is given by weight of the catalyst.

[0121] Comparative Example 1

[0122] Pseudo-boehmite 200 g, Panniset 4.0 g, and silica 3.6 g, silica sol (SiO2 content 40%) 10 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, and acetic acid 2.0 g were dissolved in water to make a solution of 205 ml. The solution was added to the kneader and kneading was continued for 40 minutes, after which the wet strip was extruded in the shape of clover leaves of 1 mm in size. The wet strip was dried at 130°C for 24 hours and then calcined at 700°C for 5 hours to obtain the support Z7. The composition of catalyst C12 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide and phosphorus pentoxide is given by weight of the catalyst.

[0123] Ammonium molybdate 9.21 g, nickel acetate 63.99 g, phytic acid 6.28 g, and citric acid 15 g were dissolved in water to make an impregnation solution of 108.1 ml. 100 g of the support Z6 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 130°C for 4 hours and then calcined at 600°C for 8 hours to obtain catalyst CD1. The composition of catalyst CD1 is given in Table 4, where the content of nickel oxide, molybdenum trioxide and phosphorus pentoxide is given by weight of the catalyst.

[0124] Comparative Example 2

[0125] Pseudo-boehmite 200 g, Panniset 4.0 g, and silica 3.6 g, silica sol (SiO2 content 40%) 10 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, and acetic acid 2.0 g were dissolved in water to make a solution of 205 ml. The solution was added to the kneader and kneading was continued for 40 minutes, after which the wet strip was extruded in the shape of clover leaves of 1 mm in size. The wet strip was dried at 130°C for 24 hours and then calcined at 700°C for 5 hours to obtain the support Z7. The composition of catalyst C12 is given in Table 3, where the content of magnesium oxide and silicon oxide is given by weight of the support; the content of nickel oxide, molybdenum trioxide and phosphorus pentoxide is given by weight of the catalyst.

[0126] Ammonium molybdate 9.21 g, nickel acetate 63.99 g, phytic acid 6.28 g, and citric acid 15 g were dissolved in water to make an impregnation solution of 108.1 ml. 100 g of the support Z6 was impregnated with an equal amount of the impregnation solution. The impregnated support was dried at 130°C for 4 hours and then calcined at 600°C for 8 hours to obtain catalyst CD1. The composition of catalyst CD1 is given in Table 4, where the content of nickel oxide, molybdenum trioxide and phosphorus pentoxide is given by weight of the catalyst.

[0127] Comparative Example 3

[0128] Pseudo-boehmite 200 g, Pannisetum 4.0 g were mixed in a kneader. Nitric acid 2.0 g, citric acid 2.0 g, acetic acid 2.0 g, magnesium nitrate 25.0 g were dissolved in water to make up 205 ml solution. The solution was added to the kneader and kneading was continued for 40 minutes, then the kneaded mixture was extruded into 1 mm three-leaf clover shaped wet strips. The wet strips were dried at 110°C for 20 hours and then calcined at 600°C for 8 hours to obtain the support Z8. The composition of catalyst CD4 is shown in Table 4, in which the contents of magnesium oxide and silicon oxide are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0129] A mixture of 7.17 g ammonium molybdate and 5.26 g molybdenum oxide, a mixture of 18.69 g nickel acetate and 12.55 g nickel carbonate, a mixture of 1.82 g phosphoric acid and 12.23 g phytic acid, 15 g citric acid were dissolved in water to make up 105.3 ml impregnation solution. 100 g of the support Z8 was impregnated with the same amount of the impregnation solution. The impregnated support was dried at 125°C for 3 hours and then calcined at 450°C for 7 hours to obtain the catalyst CD3. The composition of catalyst CD3 is shown in Table 4, in which the content of magnesium oxide is based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0130] [Comparative Example 4]

[0131] The support Z5 was prepared by repeating Example 5.

[0132] A mixture of 7.17 g ammonium molybdate and 5.26 g molybdenum oxide, a mixture of 18.69 g nickel acetate and 12.55 g nickel carbonate, a mixture of 1.82 g phosphoric acid and 12.23 g phytic acid, 15 g citric acid were dissolved in water to make up 105.3 ml impregnation solution. 100 g of the support Z8 was impregnated with the same amount of the impregnation solution. The impregnated support was dried at 125°C for 3 hours and then calcined at 450°C for 7 hours to obtain the catalyst CD3. The composition of catalyst CD3 is shown in Table 4, in which the content of magnesium oxide is based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0133] The composition of catalyst CD4 is shown in Table 4, in which the contents of magnesium oxide and silicon oxide are based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0134] [Comparative Example 4]

[0135] The support Z5 was prepared by repeating Example 5.

[0136] A mixture of 7.17 g ammonium molybdate and 5.26 g molybdenum oxide, a mixture of 18.69 g nickel acetate and 12.55 g nickel carbonate, a mixture of 1.82 g phosphoric acid and 12.23 g phytic acid, 15 g citric acid were dissolved in water to make up 105.3 ml impregnation solution. 100 g of the support Z8 was impregnated with the same amount of the impregnation solution. The impregnated support was dried at 125°C for 3 hours and then calcined at 450°C for 7 hours to obtain the catalyst CD3. The composition of catalyst CD3 is shown in Table 4, in which the content of magnesium oxide is based on the weight of the support; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0137] The composition of catalyst CD5 is shown in Table 4, in which the contents of magnesium oxide and silicon oxide are based on the weight of the carrier; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0138] Comparative Example 6

[0139] Example 5 was repeated to prepare carrier Z5.

[0140] Forty-three point seven four grams of ammonium molybdate, six point nine one grams of nickel acetate, thirty-seven point three four grams of phytic acid and fifteen grams of citric acid were added to water to make up 106.13 ml of impregnation solution. One hundred grams of carrier Z5 were impregnated with the impregnation solution. The impregnated carrier was dried at 110°C for 3.5 hours and calcined at 550°C for 5 hours to obtain catalyst CD6.

[0141] The composition of catalyst CD6 is shown in Table 4, in which the contents of magnesium oxide and silicon oxide are based on the weight of the carrier; the contents of nickel oxide, molybdenum trioxide and phosphorus pentoxide are based on the weight of the catalyst.

[0142] Table 1

[0143] Table 2

[0144] Table 3

[0145] Table 4

[0146] Working Examples

[0147] Working Example 1

[0148] This example illustrates the use of the catalysts obtained in Examples 1-12 in the second stage of the hydroprocessing of pyrolysis gasoline. The feedstock for the second stage of hydroprocessing was the first stage hydroprocessing product of pyrolysis gasoline, which was the C6-C8 fraction of pyrolysis gasoline, and its composition and properties are shown in Table 5.

[0149] One hundred milliliters of the catalysts of Examples 1-12 were separately presulfided. The presulfiding conditions included: the sulfiding oil was a mixture of cyclohexane and dimethyl disulfide (sulfur content 3000 ppm); hydrogen was passed at a pressure of 2.8 MPa and the hydrogen volume space velocity was 300 h -1 ; the catalyst bed was heated to 160°C and the sulfiding oil was then fed in at a volume space velocity of 4.5 h -1 ; the catalyst bed was then heated at a rate of 30°C / h to 320°C and maintained for 24 hours, then cooled to 220°C and the sulfiding oil was stopped, thus completing the presulfiding.

[0150] The reaction conditions for the second-stage hydrogenation were: reaction pressure 2.8 MPa, inlet temperature 220°C, fresh feed oil space velocity 3.0 h -1 , hydrogen / oil volume ratio 400. The feed was hydrogenated for 100 hours under the above conditions in the presence of 100 mL of the catalyst of Examples 1 to 12, respectively. The second-stage hydrogenation was repeated three times, and the average of the results was taken as the test data, which is shown in Table 6-1.

[0151] Table 5 Properties of the feed

[0152] Table 6-1 Test results of the catalysts of Examples 1 to 12

[0153] [Working Example 2]

[0154] Working Example 1 was repeated using the catalysts of Examples 3, 4, 5, 8, 9 and Comparative Example 4, respectively, except that the diene value of the feed was 3, 6 and 8 g I2 / 100 g, respectively. The results are shown in Table 6-2 below.

[0155] Table 6-2 Test results of the catalysts of Examples 3 to 5, 8 to 9 and Comparative Example 4

[0156] [Working Example 3]

[0157] Working Example 1 was repeated using the catalysts of Examples 3, 6, 8 and Comparative Examples 4, 5, respectively, except that the diene value of the feed was 9 g I2 / 100 g. The results are shown in Table 6-3 below.

[0158] Table 6-3 Test results of the catalysts of Examples 3, 6, 8 and Comparative Examples 4, 5

[0159] [Working Example 4]

[0160] Working Example 1 was repeated using 100 mL of each of the catalysts of Comparative Examples 1 to 6, and the results are shown in Table 6-4.

[0161] Table 6-4 Test results of the catalysts of Comparative Examples 1 to 6

[0162] [Working Example 5]

[0163] This example illustrates the stability of the catalysts of Example 3 and Example 7 in the second-stage hydrogenation treatment of pyrolysis gasoline.

[0164] Example 1 was repeated using 100 ml of the above catalyst. The difference was that the second-stage hydrogenation reaction conditions were: hydrogen pressure 2.8 MPa, inlet temperature 220°C, fresh oil space velocity 3.0 h"1, hydrogen / oil volume ratio 400. The feedstock was hydrogenated under the above conditions for 1000 hours in the presence of 100 ml of the catalyst. The results of the second-stage hydrogenation were repeated three times, and the average values of the results were taken as the test data, which are shown in Table 7. -1 Example 1 was repeated using 100 ml of the above catalyst. The difference was that the second-stage hydrogenation reaction conditions were: hydrogen pressure 2.8 MPa, inlet temperature 220°C, fresh oil space velocity 3.0 h"1, hydrogen / oil volume ratio 400. The feedstock was hydrogenated under the above conditions for 1000 hours in the presence of 100 ml of the catalyst. The results of the second-stage hydrogenation were repeated three times, and the average values of the results were taken as the test data, which are shown in Table 7.

[0165] Table 7 Test results of the catalysts of Examples 3 and 7

[0166] The above detailed description of the specific embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A hydrogenation catalyst characterized by, The hydrogenation catalyst comprises an active component and a carrier, wherein the active component is composed of Ni, Mo and P, and the carrier is a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide; the mass ratio of Ni and Mo in the active component is 1.1-5, preferably 1.9-2.3, based on the weight of the hydrogenation catalyst, wherein Ni is calculated as NiO and Mo is calculated as MoO3.

2. The catalyst according to claim 1, characterized in that, The hydrogenation catalyst comprises 10.0-20.0% of Ni, calculated as NiO; 5.0-10.0% of Mo, calculated as MoO3; and 1.0-5.0% of P, calculated as P2O5, based on the total weight of the hydrogenation catalyst; preferably comprises 12.0-18.0% of Ni, calculated as NiO; 5.2-7.8% of Mo, calculated as MoO3; and 2.0-5.0% of P, calculated as P2O5, as the active component.

3. The catalyst of claim 1, wherein The composite oxide comprises 90.0-98.0% of aluminum oxide, 1.0-5.0% of silicon oxide and 1.0-5.0% of magnesium oxide, based on the weight of the composite oxide; preferably comprises 91.0-93.0% of aluminum oxide, 4.7-5.0% of silicon oxide and 2.3-3.7% of magnesium oxide.

4. The catalyst of claim 1, wherein The catalyst has a (BET) specific surface area of 150-250 m 2 / g and a total pore volume of 0.4-0.6 ml / g; preferably a (BET) specific surface area of 180-249 m 2 / g and a total pore volume of 0.50-0.59 ml / g.

5. The catalyst of claim 1, wherein The percentage of the desorption peak area corresponding to the acid sites at 150-250℃ to the total desorption peak area in the NH3-TPD curve of the hydrogenation catalyst is 60-80%, preferably 65-75%, and the percentage of the desorption peak area corresponding to the acid sites at 250-450℃ to the total desorption peak area is 20-40%; preferably 22-26%.

6. A method for preparing a hydrogenation catalyst, comprising the following steps: (A) providing a composite oxide comprising magnesium oxide, aluminum oxide and silicon oxide; (B) preparing an impregnation solution with a Ni source, a Mo source and a P source, impregnating the composite oxide in the impregnation solution, and performing first drying and first calcination on the impregnated composite oxide to obtain the hydrogenation catalyst.

7. The preparation method according to claim 6, characterized in that The step (A) of providing a composite oxide comprises the following steps: (1) mixing a magnesium source, water and at least one acid selected from citric acid, nitric acid and acetic acid to obtain solution A; and (2) mixing an aluminum source, a silicon source, an organic additive and solution A, shaping the mixture, performing second drying and second calcination to obtain the composite oxide.

8. The preparation method according to claim 7, characterized in that The magnesium source is at least one selected from magnesium sulfate, magnesium chloride, magnesium nitrate and magnesium acetate; the silicon source is at least one selected from silicon oxide and silica sol; the aluminum source is at least one selected from pseudoboehmite, boehmite, gibbsite and bayerite, preferably pseudoboehmite; the organic additive is at least one selected from sesbania gum, carboxymethyl cellulose, polyvinyl alcohol and starch, preferably sesbania gum; and / or The second drying is performed at 50-200℃ for 6-36h, preferably at 100-130℃ for 12-24h; and the second calcination is performed at 400-1000℃ for 2-12h, preferably at 500-800℃ for 4-8h.

9. The preparation method according to claim 6, characterized in that the Ni source is at least one of nickel nitrate, nickel acetate and nickel carbonate; the Mo source is at least one of ammonium molybdate and molybdenum oxide; the P source is at least one of phosphoric acid or phytic acid; and / or the first drying is carried out at 50-150°C for 1-6h, preferably at 100-130°C for 2-4h; the first calcination is carried out at 400-800°C for 2-12h, preferably at 400-600°C for 4-8h.

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

11. Use of a hydrogenation catalyst according to any one of claims 1 to 5 and 10 for the hydrofining of petroleum hydrocarbons, preferably for the second stage hydroprocessing of pyrolysis gasoline or a fraction thereof.

12. Use according to claim 11, characterized in that, The pyrolysis gasoline comprises steam pyrolysis gasoline or thermal pyrolysis gasoline; the fraction of pyrolysis gasoline comprises a C6-C8 fraction, a C6-C9+ fraction or a C5-C9 fraction, etc.; preferably, the diene value of the pyrolysis gasoline or the fraction thereof is 3-10 g I2 / 100 g, preferably 5-8 g I2 / 100 g.

13. The use according to claim 11, characterized in that, The reaction conditions of the two-stage hydroprocessing include: using an adiabatic bed reactor, a reaction pressure not less than 2.7 MPa, an inlet temperature of 220-230°C, a fresh raw material oil space velocity of 2.0-3.0 h -1 , a hydrogen / oil volume ratio of 400-1000; and / or The catalyst is pre-sulfided before the second stage hydroprocessing is carried out.

12. A process for the hydroprocessing of pyrolysis gasoline or a fraction thereof, comprising contacting the pyrolysis gasoline or the fraction thereof with a hydrogenation catalyst according to any one of claims 1 to 5 and 10.

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