CN107971034B

CN107971034B - Vulcanization type hydrogenation catalyst, preparation method and application thereof

Info

Publication number: CN107971034B
Application number: CN201610921080.3A
Authority: CN
Inventors: 韩伟; 龙湘云; 李明丰; 杨清河; 聂红; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-21
Filing date: 2016-10-21
Publication date: 2020-05-19
Anticipated expiration: 2036-10-21
Also published as: CN107971034A

Abstract

The invention relates to the field of hydrorefining and discloses a vulcanized hydrogenation catalyst as well as a preparation method and application thereof, wherein the method comprises the following steps: (1) mixing a dispersant with a solution A containing VIB group metal salt, VIII group metal salt and a sulfur source, wherein the solution A is acidic, the dispersant is a water-soluble organic solvent with a boiling point of 15-90 ℃, and the sulfur source is a sulfur-containing substance which can be hydrolyzed under acidic conditions at 50-100 ℃; (2) contacting the mixture obtained in the step (1) with a catalyst carrier for 5-30 hours at 60-150 ℃ under a closed condition; (3) and (3) roasting the solid material obtained after the contact in the step (2) in an inert or reducing atmosphere. The method provided by the invention introduces the main agent component and the auxiliary agent component in one step, and the prepared catalyst active component is highly dispersed and fully vulcanized, so that the hydrogenation performance of the catalyst is obviously improved finally.

Description

Vulcanization type hydrogenation catalyst, preparation method and application thereof

Technical Field

The invention relates to the field of hydrofining, in particular to a preparation method of a vulcanized hydrogenation catalyst, the vulcanized hydrogenation catalyst prepared by the method and application of the vulcanized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogenation.

Background

The hydrogenation technology is the most important means for producing clean oil products, wherein the high-efficiency hydrogenation catalyst is the hydrogenation technologyThe core technology of (1). Uses VIB group metal W or Mo as main active component, VIII group metal Ni or Co as auxiliary active component and gamma-A1₂O₃Or modified gamma-A1₂O₃The supported catalyst as a carrier is a hydrogenation catalyst which is widely used in industry at present. The traditional preparation technology mainly adopts an impregnation method to introduce an oxidized precursor of an active component into a carrier pore passage, and then the hydrogenation catalyst is obtained through aging, drying and roasting. Wherein the Co, Ni, Mo and W active components are present in the form of oxides. However, in actual use, the active components of the hydrogenation catalyst exist in the form of sulfides of Co, Ni, Mo and W, so that the hydrogenation catalyst is subjected to sulfidation activation, namely presulfiding, before use.

Although the traditional preparation technology is applied to large-scale industry due to the advantages of simple operation, low cost and the like, the traditional preparation technology still has a series of problems. On the one hand, when the oxidized active component is used as a precursor, the oxidized active component reacts with Al in the impregnation aging process or the drying roasting process₂O₃The surface tends to have strong interaction, which not only easily causes uneven dispersion of the active component on the surface of the carrier, but also causes excessive generation of Al-O-Mo chemical bonds, and then causes difficulty in completely simultaneously forming excessive low-activity I-type active phases during vulcanization of the active component, and the utilization rate of the active metal is low (see CN 103143365A). In addition, taking Mo-based catalyst preparation as an example, the commonly used precursor ion Mo₇O₂₄ ^6-Tends to induce Al₂O₃Surface dissociation to produce Al³⁺Subsequently reacted therewith to form the Anderson type heteropolyanion Al (OH)₆Mo₆O₁₈ ^3-The large-grain MoO which is difficult to be fully vulcanized and is not beneficial to improving the catalytic activity is generated through roasting₃And Al₂(MoO₄)₃Species (see J.A. Bergwefff et al, Journal of the American Chemical Society 2004,126: 14548; J.A. Bergwefff et al, Catalysis today2008,130:117.), and it is therefore difficult to achieve hydrogenation catalysts with both high dispersion of active components and high sulfidity using conventional impregnation techniques, resulting in less than optimal catalytic activity. On the other hand, the prevulcanization process adopted in the traditional preparation technologyThe in-situ sulfurization technology is that firstly an oxidation state catalyst is loaded into a hydrogenation reactor, then hydrogen and a sulfurizing agent are introduced into the reactor for sulfurization in the process of continuously raising the temperature, although the technology is still the most widely applied technology at present, a series of problems still exist: 1) the vulcanization time is too long, and the start-up is delayed; 2) the device is easy to corrode and age in the vulcanization process; 3) the vulcanizing agent is inflammable and toxic, and is easy to cause environmental pollution; 4) higher cost, etc. In view of the problems of the "in-plant" vulcanization technology, CN1861258A, CN1861260A, CN101088619A, CN101088620A, CN1994567A, CN101279296A, CN101491725A, US6365542 developed a series of "out-of-plant" vulcanization technologies, which mainly include two routes: the first technical route is to introduce a vulcanizing agent (elemental sulfur, vegetable oil, organic sulfide, organic polysulfide, sulfone, sulfoxide, etc.) into the voids of the hydrogenation catalyst in an oxidized state by sublimation, melting or impregnation, and then to vulcanize the catalyst by heat treatment in the presence of an inert gas; the second technical route is to complete the presulfiding of the catalyst in the oxidation state in the presence of hydrogen and hydrogen sulfide or readily decomposable organic sulfiding agents on a dedicated presulfiding unit. However, no matter the in-situ or ex-situ vulcanization is adopted, the catalyst is required to be firstly oxidized and then presulfurized, so that the preparation process of the catalyst is complex and the economic efficiency is poor.

In order to realize that the hydrodesulfurization catalyst has higher active component dispersion degree, ensure the full vulcanization of the active component, avoid the problems in the in-reactor vulcanization process and simplify the ex-reactor vulcanization route, the direct preparation route of the vulcanization type hydrodesulfurization catalyst in recent years gets more and more attention and exploration.

US6451729 non-supported MoS with high specific surface area is produced by dissolving thiomolybdic acid in organic solvent in the presence of high-temperature hydrogen₂The catalyst has high hydrocracking activity. The disadvantages of such processes are the high cost of catalyst preparation and the only possibility to prepare powdered catalysts, which cannot be used in large scale hydrogenation plants.

CN1557917A discloses a sulfide type hydrogenation catalyst and a preparation method thereof, wherein the preparation method of the catalyst mainly comprises the steps of introducing precursors of VIB group metals Mo and W into gaps of a hydrogenation catalyst carrier by adopting soluble thiomolybdate and thiotungstate solutions to the carrier of a conventional catalyst, roasting for 4 hours at 350 ℃ under the protection of nitrogen, dipping by using a solution containing Ni and Co, and roasting for 4 hours at 350 ℃ under the protection of nitrogen, thereby preparing the supported sulfide catalyst of Mo, W, Co and Ni. Although the method can prepare the hydrogenation catalyst with excellent performance, the main agent component and the auxiliary agent component are sequentially impregnated, and the preparation process is complicated, particularly the synthesis process of the vulcanization type precursor is complicated, so that the preparation cost of the catalyst is very high, and the method is not suitable for large-scale industrial application.

CN102039147A discloses a preparation method of a sulfuration type catalyst, which adopts alkyl molybdenum (tungsten) sulfide ammonium salt containing metal Mo or W, inorganic salt of Ni or Co and organic auxiliary agent as impregnation liquid, impregnates a required catalyst carrier, and directly obtains the sulfuration type catalyst by drying. The method has the advantages of simple preparation process, no need of inert gas protection in the preparation process, easy formation of II-type active phase with high catalytic activity, and high catalyst service performance, but finally has high preparation cost and low application possibility because the thio-molybdenum (tungstate) which is difficult to synthesize and has very high price is also adopted as an active precursor.

In summary, the activity of the catalyst obtained by the preparation method of the sulfidation type hydrogenation catalyst provided by the prior art is improved, but the improvement degree is limited, and the preparation method of the sulfidation type hydrogenation catalyst has the defects that a main agent component and an auxiliary agent component need to be respectively introduced into a carrier, the preparation route is complex, the controllability is poor, and the cost is high, so that the industrial application of the methods is limited to a certain extent.

Disclosure of Invention

Aiming at the defects of lower activity, more complex preparation process, poorer controllability and higher cost of the vulcanized hydrogenation catalyst in the prior art, the invention provides a novel preparation method of the vulcanized hydrogenation catalyst, the vulcanized hydrogenation catalyst obtained by the method and the application of the vulcanized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogenation.

The invention provides a preparation method of a vulcanized hydrogenation catalyst, which comprises the following steps:

(1) mixing a dispersant with a solution A containing VIB group metal salt, VIII group metal salt and a sulfur source, wherein the solution A is acidic, the dispersant is a water-soluble organic solvent with a boiling point of 15-90 ℃, and the sulfur source is a sulfur-containing substance which can be hydrolyzed under acidic conditions at 50-100 ℃;

(2) contacting the mixture obtained in the step (1) with a catalyst carrier for 5-30 hours at 60-150 ℃ under a closed condition;

(3) and (3) roasting the solid material obtained after the contact in the step (2) in an inert or reducing atmosphere.

The invention also provides a vulcanization type hydrogenation catalyst prepared by the method and application thereof in hydrodesulfurization and/or hydrodenitrogenation.

According to the method provided by the invention, the prepared catalyst is in a vulcanized state and does not need to be vulcanized again when in use. At present, most research results consider that MoS is directly in the main agent₂/WS₂The addition of Co or Ni as assistant is favorable to forming Co (Ni) -Mo (W) -S active phase structure and thus has excellent hydrogenating performance (see Okamoto et al journal of Catalysis 2004222: 143). Therefore, when the sulfided hydrogenation catalyst is prepared in the prior art, the group VIB metal salt is firstly added to the carrier, and then the group VIII metal is introduced, for example, in the preparation method of the sulfided hydrogenation catalyst disclosed in CN1557917A, the group VIB metals Mo and W are firstly introduced to the carrier, and the group VIII metals Co and Ni are introduced after calcination. The inventor of the present invention has surprisingly found in the research process that in the preparation process of the sulfidation type hydrogenation catalyst, the catalyst with good hydrogenation performance can be prepared by introducing the VIB group metal salt and the VIII group metal salt into the carrier together in the presence of the sulfur source and the dispersant. The reason for this is probably because the present invention directly contains the VThe solution of the sulfur source of the IB group metal salt and the VIII group metal salt is mixed with a dispersant and then contacted with a catalyst carrier under specific conditions, the VIB group metal is diffused and deposited on the surface of the carrier in the form of trisulfide nano particles, while the group VIII metal diffuses-deposits to the support surface in the form of hydrated cations, because the trisulfide nano-particles have certain electronegativity in aqueous solution, once the nano-particles are generated, the surrounding hydrated cations of the VIII group metal are necessarily adsorbed to the surface of the trisulfide nano-particles uniformly, thereby promoting the synchronous and uniform diffusion-deposition of the metals of the VIB group and the VIII group on the surface of the carrier pore canal, this creates conditions for promoting more of the group VIII metal as promoter atom to enter into the corner position of the group VIB metal sulfide as main agent atom to form more Co (Ni) -Mo (W) -S. Therefore, the situation that the assistant effect is not ideal because the assistant VIII metal is vulcanized before the main agent VIB metal in the conventional preparation process is effectively avoided, and the vulcanized hydrogenation catalyst is ensured to maintain higher activity. Preferably, the catalyst carrier is modified by using the water-soluble divalent metal salt in the aqueous solution containing the urea, so that the activity of the catalyst can be improved, and the high activity of the catalyst can be effectively maintained for a long time, thereby greatly prolonging the service life of the catalyst. The reason for this is presumably because the introduction of a water-soluble divalent metal salt into the aqueous solution containing urea can be used to modify the surface structure of the catalyst support in addition to the active component, so that the surface of the support forms a "network" structure (as shown in FIG. 2) which is favorable for efficient dispersion and anchoring of the active component. And the subsequent introduction of the metal hydrogenation active component, the surface of the catalyst still maintains the 'net' structure (as shown in figure 3). The 'net-shaped' structure is not only beneficial to the loading, dispersion and anchoring of the active metal component, but also effectively weakens the strong interaction between the active component and the carrier.

The preparation method of the vulcanization type hydrogenation catalyst provided by the invention effectively avoids the defect of non-ideal auxiliary effect under the condition of introducing the VIB group metal and the VIII group metal in one step, is simple and convenient in operation process, has high dispersion degree and high vulcanization degree of active components, and improves the hydrogenation performance of the catalyst. Meanwhile, CN1557917A mentions that the catalyst loaded with Mo, W, Co and Ni low valence sulfides is safe, non-pyrophoric and non-pyrophoric at room temperature and in relatively dry air, so that the catalyst prepared by the method of the invention can ensure the safety of the catalyst in the processes of storage, transportation and filling as long as the catalyst is treated by inert gas and is packaged in a closed and light-tight manner at room temperature.

Compared with the prior art, the preparation method of the vulcanization type hydrogenation catalyst provided by the invention is simple to operate, easy to repeat, low in catalyst preparation cost, good in hydrogenation performance of the prepared catalyst, free of pre-vulcanization, capable of saving the start-up time and friendly to the environment.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 shows unmodified γ -Al from example 1₂O₃SEM image of the support surface;

FIG. 2 is an SEM image of the surface of a Z-1 Co-modified alumina support of example 1;

FIG. 3 is an SEM photograph of the surface of a sulfided hydrogenation catalyst S-1 in example 1.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, preferably, the group VIII metal is cobalt and/or nickel, and the group VIB metal is molybdenum and/or tungsten.

In the present invention, preferably, the group VIB metal salt is selected from one or more of sodium molybdate, sodium tungstate, ammonium paramolybdate, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate; the group VIII metal salt is selected from one or more of water soluble cobalt and/or nickel nitrate, carbonate, chloride, sulfate and acetate.

According to the invention, the concentration of the group VIB metal salt in solution A is preferably from 0.005 to 5mol/L, preferably from 0.05 to 0.3mol/L, more preferably from 0.15 to 0.3 mol/L.

In the present invention, the molar ratio of the group VIII metal element to the group VIB metal element is preferably 0.1 to 1.5, and more preferably 0.15 to 0.5. With this preferred embodiment it is more beneficial to exert a synergistic effect of the group VIII and group VIB metals and to the formation of the active phase.

According to the present invention, the dispersant may be various water-soluble organic solvents having a boiling point of 15 to 90 ℃, preferably one or more selected from methanol, ethanol, propanol and acetone, more preferably ethanol.

The selection range of the adding amount of the dispersing agent is wide, and the volume ratio of the adding amount of the dispersing agent to the solution A is preferably 0.1-10: 1, more preferably 0.5 to 2: 1.

according to the present invention, the sulfur source may be various sulfur-containing substances that can be hydrolyzed under acidic conditions at 50 to 100 ℃, and preferably the sulfur source is at least one selected from the group consisting of thioamides represented by the following formula (1), monothioesters represented by the formula (2), and dithioesters represented by the formula (3),

in the formula (1), R¹Is NH₂-、CH₃-、CH₃CH₂-、CH₃NH-or (CH)₃)₂N-，R²And R³Each independently is H or C1-C4 alkyl; in the formula (2), R⁴Is H or C1-C4 alkyl, R⁵Is C1-C4 alkyl; in the formula (3), R⁶Is H or C1-C4 alkyl, R⁷Is a C1-C4 alkyl group, said C1-C4 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. R²And R³May be the same or different. More preferably, the sulfur source is a thioamide represented by formula (1), still more preferably, the sulfur source is thiourea and/or thioacetamide, and most preferably, the sulfur source is thioacetamide.

In the invention, the adding amount of the sulfur source is based on the condition that the VIB group metal and the VIII group metal are fully sulfurized, and preferably, the molar ratio of the sulfur source to the VIB group metal elements is 1-9: 1, more preferably 3 to 5: 1, most preferably 3: 1.

in the present invention, acidic means a pH value of less than 7. According to the invention, the solution A can be made acidic in various ways, for example by adding organic and/or inorganic acidic substances, preferably hydrochloric acid and/or nitric acid.

In the present invention, although it is sufficient to make the solution A acidic, it is preferable that the pH of the solution A is not more than 5, more preferably 2 to 5. For hydrochloric acid and nitric acid, the pH can be controlled within the above range by controlling the molar ratio of the acid addition to the group VIB metal to be 0.5-3.

In the present invention, the solvent forming the solution a is preferably water.

Preferably, the mixing in step (1) is performed under stirring conditions, so that the group VIB metal salt, the group VIII metal salt and the sulfur source are mixed more thoroughly and uniformly. The stirring speed may be 10-500 rpm.

The dispersant is preferably mixed with the solution a containing the group VIB metal salt, the group VIII metal salt and the sulfur source by adding the dispersant dropwise to the solution a. The rate of addition is preferably 1 to 5ml/min relative to 0.1 moles of group VIB metal salt.

According to a preferred embodiment of the present invention, before step (2), the catalyst support is modified by a method comprising: the catalyst carrier is soaked in a mixture containing urea, water-soluble divalent metal salt and water, and then is sequentially subjected to heat treatment, filtration, washing, drying and roasting.

By adopting the preferred embodiment, the surface of the carrier has a net structure, which is beneficial to efficiently dispersing and anchoring active components, and after the metal hydrogenation active components are introduced subsequently, the surface of the catalyst still maintains the net structure, and the net structure is beneficial to loading, dispersing and anchoring the active metal components and also effectively weakens the strong interaction between the active components and the carrier.

According to the present invention, the concentration of the water-soluble divalent metal salt in the mixture used in the modification step is preferably 0.01mol/L to 1mol/L, and more preferably 0.1mol/L to 0.5 mol/L.

According to the present invention, preferably, the water-soluble divalent metal salt is selected from one or more of nitrate, sulfate and chloride salts of divalent metals.

The divalent metal may be selected from one or more of group VIII metals, group iia metals, group ib metals and group iib metals.

In the present invention, the group VIII metal element may be one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum elements.

The group IIA metal element may be one or more of calcium, magnesium, strontium and barium.

The group IB metal element may be copper and/or gold.

The group IIB metal element may be zinc and/or cadmium.

Preferably, the divalent metal element is selected from one or more of cobalt, nickel, iron, calcium, magnesium, copper and zinc elements.

According to the invention, the molar ratio of urea to water-soluble divalent metal salt in the mixture is preferably 2-10: 1.

According to the invention, the molar ratio of the catalyst support to the water-soluble divalent metal salt in the mixture is 3 to 20: 1, more preferably 4 to 10: 1.

according to the present invention, preferably, the heat treatment conditions include a heat treatment temperature of 60 to 140 ℃, more preferably 70 to 90 ℃, and a heat treatment time of 2 to 60 hours, more preferably 12 to 24 hours.

The drying conditions in the modification of the catalyst support in the present invention are not particularly limited, and may be various drying conditions commonly used in the art, for example, the drying conditions include a drying temperature of 100 to 250 ℃, preferably 100 to 130 ℃, and a drying time of 1 to 12 hours, preferably 2 to 6 hours.

The calcination conditions in the modification of the catalyst support of the present invention are not particularly limited, and may be various calcination conditions commonly used in the art, for example, calcination conditions including calcination temperature may be 400 to 600 ℃, preferably 450 to 550 ℃, and calcination time may be 2 to 10 hours, preferably 2 to 6 hours.

The catalyst carrier of the present invention is not particularly limited, and may be a porous oxide carrier, for example, γ -Al₂O₃、SiO₂、TiO₂、SBA-15、ZrO₂And SiO₂-γ-Al₂O₃One or more of (a). Particularly preferably, the carrier is gamma-Al with the diameter of 2mm to 5mm₂O₃Particles or diameters in2mm to 5mm of SiO₂-γ-Al₂O₃And (3) granules. The above-mentioned carrier can be obtained commercially, or can be prepared by a conventional method.

In the present invention, the adding amount of the catalyst carrier in the step (2) is not particularly limited, and those skilled in the art can select the catalyst carrier according to actual situations, and details thereof are not repeated herein. Preferably, the catalyst carrier is added in an amount such that the prepared hydrogenation catalyst contains, based on the total amount of the catalyst, 5 to 35 wt%, more preferably 10 to 30 wt%, of the group VIB metal, 1 to 11 wt%, more preferably 2 to 5 wt%, of the group VIII metal, and 60 to 90 wt%, more preferably 65 to 85 wt% of the carrier.

In the present invention, the contacting in step (2) is preferably carried out in an autoclave. The autoclave is 10 affordable⁹A pressure of Pa.

Preferably, in the step (2), the mixture obtained in the step (1) is contacted with the catalyst carrier under a closed condition at 80-120 ℃ for 8-24 hours.

It is further preferred that the contacting in step (2) is carried out under stirring. Stirring can be achieved by placing the autoclave in a rotary oven through rotation of the rotary oven. The rotational speed of the rotary oven may be 30-200 rpm.

According to the invention, solid materials are obtained by preferably filtering, washing and drying the materials obtained by contacting in the step (2).

The conditions for the filtration, washing with water and drying are not particularly limited in the present invention, and may be various types conventionally used in the art, and those skilled in the art can select the conditions by specific conditions.

The drying may be drying at room temperature, drying in an oven (preferably under an inert atmosphere), or vacuum drying.

According to the present invention, the inert atmosphere may be selected from one or more of nitrogen, argon and helium, preferably nitrogen.

According to the invention, the reducing atmosphere may be selected from gases containing hydrogen and/or hydrogen sulphide.

The reducing atmosphere may contain an inert gas, and when the inert gas is contained in the reducing atmosphere, the volume content of hydrogen and/or hydrogen sulfide is not less than 5%.

According to the invention, the impregnated solid material of step (3) is preferably calcined in a reducing atmosphere, most preferably in a hydrogen atmosphere. This preferred mode is more advantageous in increasing the activity of the catalyst.

In the present invention, the conditions for the calcination in the step (3) are not particularly limited, and preferably the calcination conditions include: the roasting temperature is 300-800 ℃, and the roasting time is 2-6 hours; further preferably, the calcination temperature is 400 to 600 ℃ and the calcination time is 3 to 5 hours.

The sulfide type hydrogenation catalyst prepared by the preparation method has excellent hydrodesulfurization and denitrification activity, so the invention also provides the sulfide type hydrogenation catalyst prepared by the preparation method and the application thereof in hydrodesulfurization and/or hydrodenitrification.

The sulfided hydrogenation catalyst according to the invention has a group VIB metal content of 5 to 35 wt.%, preferably 10 to 30 wt.%, a group VIII metal content of 1 to 11 wt.%, preferably 2 to 5 wt.%, and a support content of 60 to 90 wt.%, preferably 65 to 85 wt.%, based on the respective metal oxide, based on the total amount of the catalyst.

According to a preferred embodiment of the invention, the surface of the sulphided hydrogenation catalyst has a network structure with a grid density of 0.5 to 50 cells per square micron, said grid density being determined by averaging the number of grids distributed per square micron area in at least 20 sem pictures.

According to the invention, the mesh density of the mesh structure is preferably 5 to 20 pieces per square micrometer.

In the present invention, the number of the scanning electron micrographs to be taken is not particularly limited, and the grid density is preferably measured by averaging the number of grids distributed in an area of square micrometers in 30 to 50 scanning electron micrographs.

In the invention, the scanning electron microscope picture is obtained by adopting an S250MK3 type scanning electron microscope under the working condition of 20kV, the sample current is 100mA, and the working distance is 24 mm.

The preparation method of the sulfide type hydrogenation catalyst provided by the invention can be explained as that firstly, trisulfide nano particles of group VIB metals such as Mo and/or W are synthesized in a solution containing group VIII metals such as Co and/or Ni cations by adopting a chemical deposition method to obtain a solid-liquid mixed system in which Co and/or Ni cations and trisulfide nano particles of Mo and/or W coexist, then the Co-deposition is carried out on the surfaces of carrier pore channels at a certain temperature, and the solid-liquid mixed system is filtered, dried and converted into corresponding sulfides by heat treatment in inert or reducing gas.

Specifically, when the sulfur source (thioacetamide is taken as an example), molybdenum salt or tungsten salt (sodium molybdate is taken as an example), nickel salt or cobalt salt (nickel nitrate is taken as an example), H⁺In the case of nitric acid, and a carrier in the case of gamma-Al₂O₃For example) in the same solution, with thioacetamide, at low temperature and under acidic conditions, slowly hydrolyzing to generate H₂The characteristic of S is that the solution temperature is controlled to continuously generate chemical reaction to generate MoS₃Grains of crystal to obtain Ni²⁺And MoS₃Solid-liquid suspension system with coexisting crystal grains, each of which is electronegative MoS due to electrostatic adsorption₃Ni is adsorbed around the nano crystal grains²⁺Formation of Ni-MoS₃Composite particles, then Ni²⁺-MoS₃The composite particles are diffused and deposited on the surface of a carrier pore channel to obtain a catalyst precursor-Ni-MoS₃/γ-Al₂O₃Finally, it is converted into the corresponding sulfide NiMoS by heat treatment in an inert or reducing gas (preferably a reducing gas)₂/γ-Al₂O₃The method of (1). This process can be expressed as follows:

3CH₃CSNH₂+6H₂O→3CH₃COONH₄+3H₂S↑ (1)

Ni²⁺+MoO₄ ^2-+3H₂S+2H⁺+γ-Al₂O₃→Ni-MoS₃/γ-Al₂O₃↓+4H₂O (2)

according to the method provided by the invention, the addition of the dispersing agent is one of the keys for achieving the purpose of the invention. This is probably because low-boiling dispersants such as methanol, ethanol or acetone, on the one hand, can adsorb to MoS by van der Waals forces₃Grain surface, inhibiting growth thereof, thereby controlling MoS₃The size of the particles, which is a prerequisite for their ability to diffuse into the carrier channels and deposit on the channel surfaces; on the other hand, the combination of the dispersant and the water can reduce the boiling point of the reaction solution, so that the reaction solution can reach a similar hydrothermal environment at a lower reaction temperature, thereby promoting the Ni-MoS₃Diffusion and deposition into the pore channel.

The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.

In the following examples, the metal content of the catalyst was measured by X-ray fluorescence spectroscopy (XRF) using a ZSX-100e X-ray fluorescence spectrometer at a current of 50mA and a voltage of 50kV using an Rh target.

The grid density of the catalyst and carrier surface is measured by a method of calculating the average value of the number of grids distributed in each square micron area in 50 scanning electron micrographs, wherein the scanning electron micrographs are obtained by adopting an S250MK3 type scanning electron microscope, the working condition is 20kV, the sample current is 100mA, and the working distance is 24 mm.

the degree of dispersion and degree of sulfidation of the host Mo (or W) in the catalyst were determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of dispersion is expressed by the surface metal atomic ratio (Mo (W)/Al) given by the XPS analysis results, and the degree of sulfidation is obtained by processing XPS data, as described in Han et Al, Journal of materials Chemistry2012,22:25340, wherein the X-ray photoelectron spectroscopy (XPS) was performed on an ESCA Lab 250X-ray photoelectron spectrometer (VG, uk) using Al K α as a radiation source, a resolution of 0.5eV, and a binding energy of C1s (Eb 285.0eV) as an internal standard contaminating carbon.

Example 1

Preparing an aqueous solution containing 0.15mol/L of sodium molybdate, 0.06mol/L of nickel nitrate and 0.45mol/L of thioacetamide, and dropwise adding 4.0mL of 2.4mol/L of hydrochloric acid in the stirring process to obtain 40mL of solution A, wherein the pH value is 5.0;

measuring 20mL of absolute ethyl alcohol, and dropwise adding the absolute ethyl alcohol into the solution A at a speed of 1mL/min in the process of continuously stirring to form a solution B;

4.0g of gamma-Al with a diameter of 2-5mm₂O₃The particles (surface SEM picture shown in figure 1) were immersed in 20.0mL of a mixed aqueous solution containing 0.2mol/L cobalt nitrate and 1.0mol/L urea, heat-treated at 80 ℃ for 24 hours, filtered, washed and then dried at 120 ℃ for 4 hours, and calcined at 500 ℃ in a 100mL/min air stream for 4 hours to give Co-modified alumina carrier Z-1, the SEM picture of Z-1 being shown in figure 2. As can be seen from fig. 2, the surface of the Co-modified alumina carrier has a large number of network structures, and the network density is listed in table 2;

transferring the solution B into an autoclave containing the prepared alumina carrier Z-1, placing the autoclave into a rotary oven (rotating speed of 100rpm) to contact for 24 hours at 85 ℃, filtering and washing the suspension, drying at room temperature, and drying at 500 ℃ in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-1. The SEM image is shown in FIG. 3, and comparing FIG. 3 with FIG. 2, it can be seen that the "network" structure of the catalyst is substantially the same, which shows that the catalyst still maintains the "network" structure of the carrier after loading the active metal component, and the analysis results of the metal content, dispersity and sulfidity of the catalyst are shown in Table 1. The catalyst lattice densities are listed in table 2.

Example 2

Preparing an aqueous solution containing 0.20mol/L sodium tungstate, 0.1mol/L nickel acetate and 0.60mol/L thioacetamide, and dropwise adding 4.5mL of 2.4mol/L hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 4.5;

measuring 30mL of absolute ethyl alcohol, and dropwise adding the absolute ethyl alcohol into the solution A at a speed of 1mL/min in the process of continuously stirring to form a solution B;

4.0g of gamma-Al with a diameter of 2-5mm₂O₃Immersing the particles in 13.0mL of mixed aqueous solution containing 0.1mol/L nickel nitrate and 0.4mol/L urea, carrying out heat treatment at 70 ℃ for 18 hours, filtering, washing, drying at 130 ℃ for 2 hours, and roasting at 550 ℃ in 100mL/min air flow for 2 hours to obtain Ni modified alumina carrier Z-2, wherein the grid density of Z-2 is shown in Table 2;

transferring the solution B into an autoclave containing the prepared alumina carrier Z-2, placing the autoclave into a rotary oven (the rotating speed is 80rpm) to contact for 24 hours at 85 ℃, filtering and washing the suspension, vacuumizing, and drying at 500 ℃ in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-2.

The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1. The catalyst lattice densities are listed in table 2.

Example 3

Preparing an aqueous solution containing 0.20mol/L of sodium molybdate, 0.09mol/L of nickel nitrate and 0.60mol/L of thiourea, and dropwise adding 4.5mL of 2.4mol/L of hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 4.5;

4.0g of gamma-Al with a diameter of 2-5mm₂O₃The pellets were immersed in 20.0mL of a mixed aqueous solution containing 0.5mol/L magnesium nitrate and 1.0mol/L urea, heat-treated at 90 ℃ for 12 hours, filtered, washed and then dried at 100 ℃ for 6 hours, and calcined at 450 ℃ in a 100mL/min air stream for 6 hours to obtain Mg-modified alumina carrier Z-3, the lattice density of Z-3 being shown in Table 2.

Transferring the solution A into an autoclave containing the prepared alumina carrier Z-3, placing the autoclave into a rotary oven (rotating speed of 100rpm) to contact for 24 hours at 85 ℃, filtering and washing the suspension, drying at room temperature, and drying at 500 ℃ in H₂Roasting in an atmosphere for 4h to obtain a sulphideType catalyst S-3.

Example 4

Preparing an aqueous solution containing 0.30mol/L of sodium molybdate, 0.05mol/L of cobalt nitrate and 0.90mol/L of thiourea, and dropwise adding 4.5mL of 2.4mol/L of hydrochloric acid in the stirring process to obtain 20mL of solution A, wherein the pH value is 5.0;

measuring 40mL of absolute ethyl alcohol, and dropwise adding the absolute ethyl alcohol into the solution A at a speed of 1mL/min in the process of continuously stirring to form a solution B;

transferring the solution B to a container containing 4.0g of gamma-Al with a diameter of 2-5mm₂O₃Placing the autoclave in a rotary oven (rotation speed of 150rpm) at 85 deg.C for 24 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-4.

The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1. The SEM images show that the catalyst surface does not have a network structure.

Example 5

Preparing an aqueous solution containing 0.30mol/L of sodium molybdate, 0.08mol/L of cobalt acetate and 0.90mol/L of thioacetamide, and dripping 9.0mL of 2.4mol/L hydrochloric acid in the stirring process to obtain 30mL of solution A with the pH value of 2.5;

transferring the solution B to a container containing 8.0g of gamma-Al with a diameter of 2-5mm₂O₃Placing the autoclave in a rotary oven (rotation speed 50rpm) at 85 deg.C for 24 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-5.

Example 6

Preparing an aqueous solution containing 0.20mol/L of sodium molybdate, 0.05mol/L of nickel nitrate and 0.60mol/L of thioacetamide, and dropwise adding 3.0mL of 2.4mol/L hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 5.0;

transferring the solution B to a container containing 2.0g of gamma-Al with a diameter of 2-5mm₂O₃Placing the autoclave in a rotary oven (rotating speed of 60rpm) at 85 deg.C for 24 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂Roasting for 4h in the atmosphere to obtain the sulfide catalyst S-6.

Example 7

Preparing an aqueous solution containing 0.20mol/L of sodium molybdate, 0.06mol/L of nickel nitrate and 0.60mol/L of thiourea, and dropwise adding 5.0mL of 2.4mol/L of hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 4.0;

measuring 30mL of absolute ethyl alcohol, and dropwise adding the absolute ethyl alcohol into the solution A at a speed of 2mL/min in the process of continuously stirring to form a solution B;

transferring the solution B to a container containing 5.0g of gamma-Al with a diameter of 2-5mm₂O₃Placing the autoclave in a rotary oven (rotation speed of 200rpm) at 105 deg.C for 20 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂And roasting for 4 hours in the S atmosphere to obtain the sulfide catalyst S-7.

Example 8

Preparing an aqueous solution containing 0.20mol/L of sodium molybdate, 0.05mol/L of nickel nitrate and 0.60mol/L of thiourea, and dropwise adding 5.0mL of 2.4mol/L of hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 4.0;

measuring 30mL of absolute ethyl alcohol, and dropwise adding the absolute ethyl alcohol into the solution A at the speed of 3mL/min in the process of continuously stirring to form a solution B;

transferring the solution B to a container containing 4.0g of gamma-Al with a diameter of 2-5mm₂O₃-SiO₂Placing the autoclave in a rotary oven (rotating speed of 100rpm) at 80 deg.C for 24 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂/H₂And roasting for 4 hours in the S atmosphere to obtain the sulfide catalyst S-8.

Example 9

Preparing an aqueous solution containing 0.20mol/L of sodium molybdate, 0.05mol/L of nickel nitrate and 0.60mol/L of thioacetamide, and dropwise adding 4.5mL of 2.4mol/L hydrochloric acid in the stirring process to obtain 30mL of solution A, wherein the pH value is 4.3;

transferring solution B to a container containing 4.0g of SiO 2-5mm in diameter₂-γ-Al₂O₃Particle (SiO)₂/γ-Al₂O₃The molar ratio is 1: 5) then the autoclave is placed in a rotary oven (rotating speed 100rpm) and contacted for 24H at 75 ℃, then the suspension is filtered, washed with water, dried at room temperature and dried at 500 ℃ in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-9.

Example 10

A sulfided hydrogenation catalyst was prepared as in example 1, except that the gamma-Al was excluded₂O₃Modifying the particles, specifically:

transferring the solution B to a container containing 4.0g of gamma-Al with a diameter of 2-5mm₂O₃Placing the autoclave in a rotary oven (rotating speed of 100rpm) at 85 deg.C for 24 hr, filtering the suspension, washing with water, air drying at room temperature, and drying at 500 deg.C in H₂Roasting for 4 hours in the atmosphere to obtain the sulfide catalyst S-10. The results of the analysis of the metal content, the dispersity and the degree of sulfidation in the catalyst are shown in Table 1. The SEM images show that the catalyst surface does not have a network structure.

Comparative example 1

Preparing NiMo/gamma-Al by normal temperature isovolumetric immersion method₂O₃A catalyst. The method specifically comprises the following steps: weighing 1.25g of ammonium molybdate tetrahydrate to prepare about 10mL of impregnation liquid, dropwise adding a small amount of hydrochloric acid to the pH value of about 4.5, and dropwise adding the solution to 10g of gamma-Al which is in a vacuum state and has the diameter of 2-5mm₂O₃Placing in a carrier, standing at room temperature until it is naturally dried, then placing in an oven, drying at 120 deg.C for 10h, and calcining at 500 deg.C for 4h to obtain Mo/Al₂O₃(ii) a Weighing 0.67g of nickel nitrate to prepare 8mL of impregnation liquid, impregnating at room temperature for 12h, drying at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain NiMo/gamma-Al₂O₃Then 1g of NiMo/gamma-Al is taken₂O₃Loading into a micro hydrogenation reactor for in-situ vulcanization, wherein the vulcanization conditions are as follows: 4.0MPa, 300 ℃, 4h, a hydrogen-oil volume ratio of 300, an oil inlet flow of vulcanized oil of 8mL/h, obtaining a catalyst D-1 after vulcanization, and the analysis results of the metal content, the dispersity and the vulcanization degree in the catalyst are listed in Table 1. The SEM images show that the catalyst surface does not have a network structure.

Comparative example 2

Preparation of CoMo/gamma-Al by normal-temperature isometric immersion method₂O₃A catalyst. The method specifically comprises the following steps: weighing 1.25g of ammonium molybdate tetrahydrate to prepare about 10mL of impregnation liquid, and dropwise adding a small amount of hydrochloric acid to the pH valueAbout 4.5, this solution was added dropwise to 10g of γ -Al having a diameter of 2 to 5mm in a vacuum state₂O₃Placing in a carrier, standing at room temperature until it is naturally dried, then placing in an oven, drying at 120 deg.C for 10h, and calcining at 500 deg.C for 4h to obtain Mo/Al₂O₃(ii) a Weighing 0.67g of cobalt nitrate to prepare 8mL of impregnation liquid, impregnating at room temperature for 12h, drying at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain CoMo/gamma-Al₂O₃Then CoMo/gamma-Al was sulfided as described in comparative example 1₂O₃Sulfurization was carried out to obtain catalyst D-2, and the analysis results of the metal content, dispersion degree and degree of sulfurization in the catalyst are shown in Table 1. The SEM images show that the catalyst surface does not have a network structure.

Comparative example 3

Preparing NiW/gamma-Al by normal temperature isovolumetric immersion method₂O₃A catalyst. The method specifically comprises the following steps: weighing 4.80g of sodium tungstate, preparing about 10mL of impregnation liquid, and dropwise adding the impregnation liquid into 10g of gamma-Al which is in a vacuum state and has the diameter of 2-5mm₂O₃Placing in a carrier, standing at room temperature until it is naturally dried, then placing in an oven, drying at 120 deg.C for 10h, and calcining at 500 deg.C for 4h to obtain W/Al₂O₃(ii) a Weighing 0.70g of nickel nitrate to prepare 8mL of impregnation liquid, impregnating at room temperature for 12h, drying at 120 ℃ for 10h, and roasting at 500 ℃ for 4h to obtain NiW/gamma-Al₂O₃Catalyst D-3, the results of the analysis of the metal content, the degree of dispersion and the degree of sulfidation in the catalyst are given in Table 1. The SEM images show that the catalyst surface does not have a network structure.

Comparative example 4

A sulfided catalyst was prepared as in example 1, except that solution A was directly contacted with Co-modified alumina support Z-1 in an autoclave, i.e., without the addition of absolute ethanol to prepare solution B, to provide sulfided catalyst D-4.

Comparative example 5

A sulfided catalyst was prepared as in example 1, except that hydrochloric acid was not added to prepare solution A, and the pH of the resulting solution was 7.0, to give sulfided catalyst D-5.

TABLE 1 analysis results of the metal content, dispersity and sulfidity of the catalyst

TABLE 2 lattice Density of catalyst and support

Sample numbering	Grid Density (micron/square)
		γ-Al₂O₃	0
Z-1	8.9
		Z-2	6.9
Z-3	9.6
		S-1	8.6
S-2	6.4
		S-3	9.2
D-4	6.5
		D-5	8.0

The lattice densities of the support and the catalyst in the remaining non-listed examples and comparative examples mean that the surfaces of the support and the catalyst do not have a network structure.

Test examples

In the present test example, the desulfurization and denitrification activities of the hydrogenation catalyst prepared by the method of the present invention and the hydrogenation catalyst provided in the comparative example were evaluated in accordance with the following methods, and the results were listed.

Hydrodesulfurization: a cyclohexane solution containing 1% by mass of Dibenzothiophene (DBT) was used as a raw material, and the desulfurization activity of the catalyst was evaluated on a WFSP3050 continuous high-pressure reactor manufactured by Naojin Kagaku Kogyo Co. The catalysts S-1 to S-10 do not need to be presulfided before reaction. The reaction conditions are as follows: 4.0MPa, 340 ℃, the volume ratio of hydrogen to oil is 300, and the oil inlet flow is 8 mL/h. After the reaction is stabilized for 3 hours, the reaction is carried out for 4 hours and the sampling is carried out after the reaction is carried out for 1000 hours, a sample is analyzed by an HS-500 type high-frequency infrared sulfur and nitrogen measuring instrument, the activity is expressed by the desulfurization rate of DBT, and the result is shown in Table 3.

And (3) hydrodenitrogenation: the denitrification activity of the catalyst was evaluated on a WFSP3050 continuous high-pressure reactor manufactured by Warit instruments of Tianjin, using an n-heptane solution containing 1% by mass of quinoline (Q) as a raw material. The catalysts S-1 to S-10 do not need to be presulfided before reaction. The reaction conditions are as follows: 4.0MPa, 340 ℃, the volume ratio of hydrogen to oil is 400, and the oil inlet flow is 8 mL/h. After the reaction is stable for 3 hours, the reaction is carried out for 4 hours and the reaction is carried out for 1000 hours, then samples are taken, the samples are analyzed by an HS-500 type high-frequency infrared sulfur and nitrogen measuring instrument, the activity is expressed by the denitrification rate of Q, and the results are shown in Table 3.

The reaction desulfurization (nitrogen) rate X is calculated as follows:

TABLE 3 evaluation results of hydrodesulfurization and denitrogenation activities of the catalysts

Note: "-" indicates no detection.

As can be seen from the results in tables 1, 2 and 3, compared with the hydrogenation catalyst prepared by the conventional method, the sulfided hydrogenation catalyst prepared by the present invention has better active component dispersion degree, higher sulfidation degree, and fully improved utilization rate of active metal, and preferably, the catalyst surface has a net structure, and more importantly, although the compositions of the two types of catalysts are similar, the catalyst provided by the present invention has significantly better hydrodesulfurization and denitrification activities. The above results are sufficient to show that the preparation provided by the present invention has advantages that are not comparable to conventional impregnation methods. Furthermore, it can be seen from comparative examples 4 and 5 that, in the present invention, the dispersant and the acidic solution are key factors for ensuring the successful implementation of the catalyst preparation route. It can be seen from the comparison of example 1 and example 10 that the catalyst service life can be effectively extended by the preferred embodiment of the present invention. In addition, the method provided by the invention introduces the main agent component and the auxiliary agent component into a simplified preparation process in one step, and overcomes the defects of more complex preparation process, poorer controllability and higher cost in the prior art.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A method for preparing a sulfided hydrogenation catalyst, the method comprising the steps of:

(3) roasting the solid material obtained after the contact in the step (2) in an inert or reducing atmosphere;

the method further comprises the following steps: prior to step (2), modifying the catalyst support by a method comprising:

the catalyst carrier is soaked in a mixture containing urea, water-soluble divalent metal salt and water, and then is sequentially subjected to heat treatment, filtration, washing, drying and roasting.

2. The production method according to claim 1, wherein the volume ratio of the added amount of the dispersant to the solution a is from 0.1 to 10: 1.

3. the preparation method according to claim 1, wherein the dispersant is selected from one or more of methanol, ethanol, propanol, and acetone.

4. The preparation method according to claim 1, wherein the pH value of the solution A is 2-5, and the concentration of the VIB group metal salt in the solution A is 0.005-5 mol/L.

5. The preparation method according to claim 1, wherein the molar ratio of the sulfur source to the group VIB metal element is 1-9: 1; the molar ratio of the VIII group metal element to the VIB group metal element is 0.1-1.5.

6. The preparation method according to claim 1, wherein the molar ratio of the sulfur source to the group VIB metal element is 3-5: 1; the molar ratio of the VIII group metal element to the VIB group metal element is 0.15-0.5.

7. The production method according to claim 1, wherein the sulfur source is at least one selected from the group consisting of a thioamide represented by the following formula (1), a monothioester represented by the formula (2), and a dithioester represented by the formula (3),

in the formula (1), R¹Is NH₂-、CH₃-、CH₃CH₂-、CH₃NH-or (CH)₃)₂N-，R²And R³Each independently is H or C1-C4 alkyl;

in the formula (2), R⁴Is H or C1-C4 alkyl, R⁵Is C1-C4 alkyl;

in the formula (3), R⁶Is H or C1-C4 alkyl, R⁷Is C1-C4 alkyl.

8. The production method according to claim 7, wherein the sulfur source is a thioamide represented by formula (1).

9. The production method according to claim 7, wherein the sulfur source is thiourea and/or thioacetamide.

10. The method according to claim 1, wherein the molar ratio of urea to water-soluble divalent metal salt is 2-10: 1.

11. the production method according to claim 1, wherein the molar ratio of the catalyst support to the water-soluble divalent metal salt is 3 to 20: 1.

12. the production method according to claim 1, wherein the molar ratio of the catalyst support to the water-soluble divalent metal salt is 4 to 10: 1.

13. the production method according to any one of claims 1 and 10 to 12, wherein the mixture used in the modification step has a concentration of a water-soluble divalent metal salt selected from one or more of nitrates, sulfates and chlorides of divalent metals selected from one or more of group VIII metals, group iia metals, group ib metals and group iib metals in the range of 0.01mol/L to 1 mol/L.

14. The production method according to any one of claims 1 and 10 to 12, wherein the divalent metal is selected from one or more of cobalt, nickel, iron, calcium, magnesium, copper, and zinc.

15. The production method according to claim 1, wherein the heat treatment conditions include a heat treatment temperature of 60 to 140 ℃ and a heat treatment time of 2 to 60 hours; the drying conditions comprise that the drying temperature is 100-250 ℃, and the drying time is 1-12 hours; the roasting conditions include the roasting temperature of 400-600 ℃ and the roasting time of 2-10 hours.

16. The production method according to claim 1, wherein the heat treatment conditions include a heat treatment temperature of 70 to 90 ℃ and a heat treatment time of 12 to 24 hours; the drying conditions comprise that the drying temperature is 100-130 ℃, and the drying time is 2-6 hours; the roasting conditions comprise that the roasting temperature is 450-550 ℃ and the roasting time is 2-6 hours.

17. The production process according to claim 1, wherein, in the step (2), the mixture obtained in the step (1) is contacted with the catalyst support under a closed condition at 80 to 120 ℃ for 8 to 24 hours.

18. The production method according to any one of claims 1 to 12, wherein the conditions for the calcination in the step (3) include: the roasting temperature is 300-800 ℃, and the roasting time is 2-6 hours.

19. A sulfided hydrogenation catalyst made by the method of any of claims 1-18.

20. Use of the sulphided hydrogenation catalyst of claim 18 in hydrodesulphurisation and/or hydrodenitrogenation.