Hydrogenation catalyst and its preparation method and application, oil product hydrogenation reaction method

Abstract

The present invention relates to the field of oil hydrogenation, and relates to a hydrogenation catalyst and a preparation method and application thereof, and a method for oil hydrogenation reaction, wherein the hydrogenation catalyst is a sulfided hydrogenation catalyst, comprising a carrier, a molecular sieve and an active component, wherein the active component comprises at least one of the metal elements of Group VIII and at least one of the metal elements of Group VIB, and the hydrogenation catalyst is characterized by a TEM-EDS method, and the amount of the molecular sieve directly acting on the metal sulfide of Group VIB accounts for 60-100% of the total amount of the molecular sieve in terms of silicon element. The hydrogenation catalyst provided by the present invention has high activity and selectivity, and can control the ring opening of polycyclic aromatic hydrocarbons without chain breaking, and generate monocyclic aromatic hydrocarbons with long branched chains, which can be used as both an ethylene cracking raw material and a high-quality diesel product.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application No. 202111278954.5 filed on October 31, 2021, the contents of which are incorporated herein by reference. Technical Field

[0003] The invention belongs to the field of oil hydrogenation, and relates to a hydrogenation catalyst and a preparation method and application thereof, and an oil hydrogenation reaction method. Background Art

[0004] In the oil processing process, according to the requirements of product quality, it is usually necessary to hydrotreat the oil products. For example, the diesel National VI or Euro VI standards require that the polycyclic aromatic hydrocarbons content in the diesel product is ≯7% or ≯8%, and polycyclic aromatic hydrocarbons need to be hydrogenated and saturated; for example, reducing diesel modification requires reducing the aromatic content in diesel and improving the cetane number of diesel products; for example, special oil product hydrogenation requires a significant reduction in the aromatic content in special oils; for example, increasing the output of chemical raw materials requires more naphtha, and hydrocracking is required to produce more naphtha. In these processes, molecular sieve-containing hydrogenation catalysts are usually used. CN200810104303.2 discloses a modified molecular sieve-based precious metal diesel deep hydrogenation and dearomatization catalyst and its preparation method, which is suitable for FCC diesel hydrogenation and dearomatization process, especially for deep hydrogenation and dearomatization of diesel after FCC diesel hydrogenation and modification, and the diesel after dearomatization can be used as a blending component of high-quality diesel. The catalyst is composed of a modified HY molecular sieve as a carrier and active components such as precious metals Pt, Pd, and Ir. Since the industrialized HY molecular sieve is modified to obtain a carrier material with a microporous-mesoporous structure and moderate acidity, and oxides of Cr, Zn, Sn, Mo, etc., which are active components with ring-opening selectivity, are added, the catalyst has the characteristics of inhibiting deep cracking and selective ring-opening performance, and the catalyst can be used for the deep dearomatization reaction of the second stage of the two-stage hydrogenation reforming of diesel. It can carry out deep dearomatization on diesel, but the carrier of the catalyst is a high-priced and high-content molecular sieve, and the active metal is a high-priced precious metal, which is too expensive. At the same time, the high-content molecular sieve carrier, most of which does not play a role.

[0005] CN201210332369.3 discloses a method for hydrogenating and converting polycyclic aromatic hydrocarbons, comprising: (1) in at least one hydrogenation reaction zone, in the presence of hydrogen, contacting a feedstock containing polycyclic aromatic hydrocarbons with a hydrogenation catalyst to react, to obtain a reaction product in which the polycyclic aromatic hydrocarbons are at least partially hydrogenated and saturated; (2) in at least one hydrocracking reaction zone, in the presence of hydrogen, contacting the reaction product in which the polycyclic aromatic hydrocarbons are at least partially hydrogenated and saturated with a hydrocracking catalyst to react; wherein the hydrogenation catalyst and operating conditions of the hydrogenation reaction zone are selected so that the conversion rate of polycyclic aromatic hydrocarbons in the feedstock containing polycyclic aromatic hydrocarbons is above 40% by weight, and the relative yield of monocyclic hydrogenated products in the product is 4-80%; the hydrocracking catalyst and operating conditions of the hydrocracking reaction zone are selected so that the conversion rate of polycyclic aromatic hydrocarbons based on the total amount of polycyclic aromatic hydrocarbons in the feedstock containing polycyclic aromatic hydrocarbons is above 85% by weight, and the relative yield of monocyclic hydrocracking products in the product is 4-30%. The method for hydrogenating and converting polycyclic aromatic hydrocarbons uses two catalysts for grading, and the molecular sieve in the carrier of the hydrocracking catalyst is added to the carrier by a mixing method. Most of the molecular sieve is wrapped by alumina and has no effect, thereby affecting the performance of the hydrocracking catalyst. Summary of the invention

[0006] In order to overcome the problem that the performance of existing hydrogenation catalysts and the utilization rate of metal active components need to be further improved, the present invention provides a hydrogenation catalyst and its preparation method and application, and a method for oil hydrogenation reaction. The hydrogenation catalyst provided by the present invention has high activity and selectivity, and can control the ring opening of polycyclic aromatic hydrocarbons without chain break to generate monocyclic aromatic hydrocarbons with long chain branches, which can be used as both ethylene cracking raw materials and high-quality diesel products.

[0007] The first aspect of the present invention provides a hydrogenation catalyst, which is a sulfide hydrogenation catalyst, comprising a carrier, a molecular sieve and an active component, wherein the active component comprises at least one of the metal elements of Group VIII and at least one of the metal elements of Group VIB. The hydrogenation catalyst is characterized by a TEM-EDS method, and the proportion of the molecular sieve directly reacting with the metal sulfide of Group VIB to the total amount of the molecular sieve is 60-100% in terms of silicon element.

[0008] Preferably, based on the total weight of the catalyst, the content of the molecular sieve is 1-20 wt%, preferably 1-12 wt%, and more preferably 1.5-8 wt%.

[0009] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the following steps:

[0010] (1) impregnating a carrier with a solution containing an organic additive, drying and calcining under an inert atmosphere to obtain a pretreated carrier;

[0011] (2) introducing a Group VIB metal salt and a Group VIII metal salt into the pretreated support by an impregnation method, and then sulfiding the pretreated support to obtain a catalyst precursor;

[0012] (3) Introducing molecular sieves into the catalyst precursor, followed by drying and calcining.

[0013] The third aspect of the present invention provides the use of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in the hydrogenation of oil products.

[0014] A fourth aspect of the present invention provides a method for hydrogenating an oil product, comprising contacting the oil product with the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect.

[0015] Preferably, the oil product contains polycyclic aromatic hydrocarbons, and the hydrogenation reaction includes a polycyclic aromatic hydrocarbon hydrogenation saturation reaction.

[0016] Compared with the prior art, the technical solution provided by the present invention has the following advantages:

[0017] (1) The catalyst of the present invention includes a carrier, a molecular sieve and an active component, and more molecular sieves act directly on the active metal, so that the utilization rate of the molecular sieve and the active metal is higher, the active effect is better exerted, and it is beneficial to reduce the amount of molecular sieve used and reduce the cost of the catalyst.

[0018] (2) The preparation method provided by the present invention prepares the catalyst in the order of carrier pretreatment - loading active metal - sulfidation - loading molecular sieve, so that more molecular sieves can directly act on the active metal and better exert the active effect.

[0019] (3) The preparation method provided by the present invention directly sulfides after impregnation with active metals and drying, and does not require a calcination process, which not only reduces the interaction between the metal oxide and the carrier, but also simplifies the process. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a high-resolution transmission electron microscopy image of the catalyst prepared in Example 1 of the present invention;

[0021] Figure 2 This is the X-ray diffraction spectrum of the catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0022] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0023] In the present invention, unless otherwise explicitly stated, percentages and contents are all based on mass.

[0024] The first aspect of the present invention provides a hydrogenation catalyst, which is a sulfided hydrogenation catalyst, comprising a carrier, a molecular sieve and an active component, wherein the active component comprises at least one of the metal elements of Group VIII and at least one of the metal elements of Group VIB. The hydrogenation catalyst is characterized by a TEM-EDS method. In terms of silicon element, the proportion of the molecular sieve directly reacting with the metal sulfide of Group VIB to the total amount of the molecular sieve is 60-100%, preferably 65%-95%, more preferably 70%-90%, and most preferably 80%-90%.

[0025] The proportion of the amount of molecular sieve directly reacting with the VIB group metal sulfide in the hydrogenation catalyst provided by the present invention to the total amount of molecular sieve is significantly higher than that of the catalyst provided in the prior art, the utilization rate of the molecular sieve and the active metal is higher, the active effect is better exerted, and it is beneficial to reduce the amount of molecular sieve used and reduce the cost of the catalyst.

[0026] In the present invention, the molecular sieve directly reacts with the Group VIB metal sulfide, which means that the molecular sieve is supported on the surface of the wafer of the Group VIB metal sulfide.

[0027] In the present invention, the amount of the molecular sieve directly interacting with the VIB group metal sulfide accounts for the total amount of the molecular sieve, the total amount of the molecular sieve (in terms of silicon element) represents the total content of the molecular sieve in the catalyst, and the amount of the molecular sieve directly interacting with the VIB group metal sulfide refers to the content of the molecular sieve within 2nm from the outermost layer of the VIB group metal sulfide wafer (in terms of silicon element). The proportion of the amount of the molecular sieve directly interacting with the VIB group metal sulfide to the total amount of the molecular sieve is characterized by the TEM-EDS (transmission electron microscope-energy dispersive X-ray spectrum) method, and the instrument model used is a Japanese JEOL JEM2200FS transmission electron microscope equipped with a scanning transmission accessory and an American EDAX company X-ray energy spectrum accessory. The electron microscope acceleration voltage is 200KV, in the STEM mode, the condenser aperture is 2, and the spot size is 0.5nm. The determination process is as follows: the catalyst particles are ground, and the sample is prepared by the suspension method. 0.1 g of the catalyst sample is placed in a 2 mL container, and ultrasonically dispersed with anhydrous ethanol. The supernatant is taken, and two to three drops are taken with a dropper and dropped on a sample net with a diameter of 3 mm. The sample to be tested is obtained after drying, and then the sample to be tested is observed and analyzed by TEM, and then the active phase (VIB group metal sulfide crystal, such as Figure 1 The Si content at a distance of less than 2 nm from the edge endpoint (as shown) is statistically analyzed, and the proportion of the amount of the molecular sieve directly interacting with the VIB group metal sulfide to the total amount of the molecular sieve is obtained based on the corresponding peak area of ​​Si. The proportion of the amount of the molecular sieve of the present invention directly interacting with the VIB group metal sulfide to the total amount of the molecular sieve is obtained by selecting 40 TEM images combined with the data obtained by EDS analysis and taking the average value.

[0028] The present invention has a wide selection range for the type and content of the molecular sieve in the catalyst, and can be appropriately selected according to different hydrogenation reactions. Different hydrogenation purposes can be achieved by controlling the type and content of the molecular sieve. For example, by controlling the type and content of the molecular sieve, the hydrogenation saturation and ring-opening and chain-breaking activity of polycyclic aromatic hydrocarbons can be accurately controlled, and the catalyst has high flexibility.

[0029] According to a preferred embodiment of the present invention, based on the total weight of the catalyst, the content of the molecular sieve is 1-20wt%, preferably 1-12wt%, more preferably 1.5-8wt%, and most preferably 2-6wt%. The present invention improves the utilization rate of the molecular sieve by increasing the proportion of the amount of the molecular sieve directly interacting with the VIB group metal sulfide to the total amount of the molecular sieve, and even at a lower molecular sieve content, the catalyst can still exert better hydrogenation performance, which is conducive to reducing the cost of the catalyst.

[0030] The present invention has no particular limitation on the method for determining the content of the molecular sieve in the catalyst. The content of the molecular sieve can be determined by combining the amount of silicon oxide with the crystal form of the molecular sieve determined by XRD, or can be calculated by feeding during the catalyst preparation process.

[0031] According to a preferred embodiment of the present invention, based on the total weight of the catalyst, the content of the VIB group metal sulfide in terms of sulfide is 10-30wt%, preferably 15-28wt%, for example, 15wt%, 17wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, and any value in the range formed by any two of these values; the content of the VIII group metal sulfide in terms of sulfide is 2-10wt%, preferably 4-8wt%, for example, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, and any value in the range formed by any two of these values. The hydrogenation catalyst provided by the present invention is a sulfided hydrogenation catalyst, and most of the active components exist in the form of sulfide. The catalyst provided by the present invention does not exclude the presence of a small amount of VIB group metal oxide and VIII group metal oxide.

[0032] The hydrogenation catalyst provided by the present invention may further contain other components. It is known that the sum of the contents of all components in the hydrogenation catalyst is 100%.

[0033] According to a preferred embodiment of the present invention, the metal element of Group VIB is Mo and / or W, and the metal element of Group VIII is Co and / or Ni. Those skilled in the art can select specific active metals for use according to specific fields.

[0034] In the present invention, the Group VIB metal sulfide may refer to MoS2 and WS2, and the Group VIII metal sulfide may refer to CoS and NiS.

[0035] In the present invention, the contents of the VIB group metal sulfide and the VIII group metal sulfide can be jointly characterized by inductively coupled plasma ICP and XPS energy spectrum. Specifically, the total content of the VIB group metal and the total content of the VIII group metal in the catalyst are first characterized by ICP, and then the content of metal elements of different valence states in the catalyst is quantitatively characterized by XPS energy spectrometer. The measurement conditions of the XPS energy spectrum include: the vacuum degree of the analysis chamber is ≤5×10 -10 mbar; vacuum degree of preparation chamber ≤1×10 -7 mbar; dual anode sensitivity 4.5×10 6 , energy resolution 1.0 eV; monochromator sensitivity 1.4×10 5The energy resolution was 0.5 eV. XPSPEAK Version 4.0 was used to fit and separate the energy spectra of Mo3d, W4f, Co2p, and Ni2p, and the contents of metal elements with different valence states in the catalyst were calculated based on the peak areas.

[0036] According to a preferred embodiment of the present invention, the molecular sieve is at least one of a Y-type molecular sieve, a ZSM-5 molecular sieve, a β-type molecular sieve and a MCM-41 molecular sieve. The molecular sieve can be commercially available or synthesized by an existing method, and the present invention has no particular limitation on this.

[0037] The present invention has no particular limitation on the carrier, and can be various carriers conventionally used in the art, can be commercially available products, or can be prepared by any method in the prior art. For example, the carrier can be an inorganic refractory oxide. Preferably, the carrier is selected from at least one of aluminum oxide, silicon oxide, titanium oxide, and zirconium oxide. Considering the cost and effect comprehensively, the carrier is preferably aluminum oxide.

[0038] In the present invention, the carrier may also contain doping elements, such as one or more of phosphorus, silicon, boron, fluorine, sodium, etc. The amount of the doping element added may be a conventional amount, preferably accounting for 0.5%-6% of the carrier mass.

[0039] A second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the following steps:

[0040] (1) impregnating a carrier with a solution containing an organic additive, drying and calcining under an inert atmosphere to obtain a pretreated carrier;

[0041] (2) introducing a Group VIB metal salt and a Group VIII metal salt into the pretreated support by an impregnation method, and then sulfiding the pretreated support to obtain a catalyst precursor;

[0042] (3) Introducing molecular sieves into the catalyst precursor, followed by drying and calcining.

[0043] According to the method provided by the present invention, by pretreating the carrier, a C inert surface layer is formed on the surface of the carrier, which can weaken the interaction between the metal and the carrier on the one hand, and on the other hand, during the introduction of the molecular sieve in step (3), because the surface of the carrier is covered with a C layer, which is non-polar, the molecular sieve will react more with the metal, thereby increasing the ratio of direct interaction between the molecular sieve and the active metal.

[0044] According to a preferred embodiment of the present invention, the carbon content in the pre-treated carrier is 3-20wt%, preferably 5-10wt%. This preferred embodiment can not only increase the ratio of direct interaction between the molecular sieve and the active metal, but also ensure the stability of the catalyst.

[0045] The present invention has no particular limitation on the type of the organic auxiliary agent, as long as it can form a C inert surface layer on the carrier surface through drying and calcination under an inert atmosphere. Preferably, the organic auxiliary agent is selected from hydrocarbons, alcohols, and carboxylic acids, and more preferably, it can be selected from at least one of ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, glucose, malonic acid, succinic acid, glutaric acid, jet fuel, and C9 aromatics.

[0046] The number of carbon atoms of the organic auxiliary agent is preferably 2 to 10. Preferably, the organic auxiliary agent contains hydroxyl and / or carboxyl groups, and this preferred embodiment is more conducive to the dispersion of active metals.

[0047] According to a preferred embodiment of the present invention, the organic auxiliary agent is selected from at least one of ethylene glycol, glycerol, butylene glycol, pentanediol, acetic acid, citric acid, glucose, malonic acid, succinic acid and glutaric acid.

[0048] According to the method provided by the present invention, the solution containing the organic additive optionally further contains a solvent. Those skilled in the art can understand that step (1) only needs to form a C inert surface layer on the surface of the carrier, and the solution containing the organic additive only needs to be able to be impregnated into the carrier. When the organic additive is a solid organic additive, it is preferred that the solution containing the organic additive further contains a solvent. When the organic additive is a liquid, the solution containing the organic additive may or may not contain a solvent.

[0049] According to the present invention, the solvent in the solution containing the organic additive has a wide selection range and is not particularly limited, as long as it can dissolve the organic additive (such as water or ethanol). Those skilled in the art can make an appropriate selection according to the specific type of organic additive.

[0050] According to a preferred embodiment of the present invention, in the solution containing an organic additive, when the organic additive is solid, the content of the organic additive is 10-30 wt %.

[0051] According to a preferred embodiment of the present invention, in the solution containing the organic additive, when the organic additive is liquid, the content of the organic additive is 50-100 wt %.

[0052] According to the present invention, the amount of the solution containing the organic auxiliary agent can be determined based on pore saturation impregnation.

[0053] The inert atmosphere in step (1) of the present invention refers to an atmosphere that does not participate in the reaction and can be provided by an inert gas, which includes but is not limited to at least one of nitrogen, helium, argon and neon.

[0054] The drying conditions in step (1) of the present invention preferably include: a temperature of 20-90° C. and a time of 4-16 hours.

[0055] The calcination conditions of step (1) of the present invention preferably include: a temperature of 200-400° C. and a time of 3-8 hours; preferably, a temperature of 250-350° C. and a time of 3-5 hours.

[0056] According to the method provided by the present invention, the selection range of the carrier and the VIB Group metal and the VIII Group metal species may be the same as the selection range of the carrier and the VIB Group metal and the VIII Group metal species in the hydrogenation catalyst described in the first aspect above, and the present invention will not be repeated here.

[0057] In the method provided by the present invention, there is no particular limitation on the impregnation method of step (2), which can be an equal volume impregnation or a supersaturated impregnation. The metal salt of Group VIB and the metal salt of Group VIII can be simultaneously introduced into the pretreatment carrier by co-impregnation, or can be separately introduced into the pretreatment carrier by step-by-step impregnation, and there is no particular limitation on the order of their introduction. Preferably, the metal salt of Group VIB and the metal salt of Group VIII are simultaneously introduced into the pretreatment carrier by co-impregnation. Preferably, step (2) comprises: impregnating the pretreatment carrier with an impregnation solution containing the metal salt of Group VIB and the metal salt of Group VIII, and then drying. Among them, the preparation method of the impregnation solution is well known to those skilled in the art. The drying is preferably carried out under an inert atmosphere. The selection range of the inert atmosphere can be the same as above and will not be repeated here. The drying conditions include: a temperature of 20-90°C and a time of 4-16 hours.

[0058] In the present invention, the types of the Group VIB metal salt and the Group VIII metal salt are selected from a wide range, based on the subsequent conversion into their respective metal sulfides. Preferably, the Group VIB metal salt is a phosphate and / or ammonium salt of a Group VIB metal, and the Group VIII metal salt is at least one of a nitrate, acetate and sulfate of a Group VIII metal.

[0059] The present invention has no particular limitation on the sulfurization in step (2), and it can be carried out by conventional methods in the art, as long as the active metal in the oxidized hydrogenation catalyst is converted into a sulfurized state. A known sulfurization method can be used, and the sulfurization is preferably dry sulfurization or wet sulfurization. The dry sulfurization and wet sulfurization in the present invention have conventional definitions in the art.

[0060] Preferably, the vulcanization conditions include: vulcanization pressure of 3.2-6.4 MPa, vulcanization temperature of 250-400°C, vulcanization time of 4-12 h, hydrogen flow rate of 2-25 mL·min -1 ·g-1 .

[0061] According to a preferred embodiment of the present invention, the dry vulcanizing agent used in the dry vulcanization is hydrogen sulfide. Specifically, the sulfide gas used in the dry vulcanization includes hydrogen sulfide and hydrogen. Preferably, the volume content of hydrogen sulfide in the sulfide gas is 1-10%.

[0062] According to a preferred embodiment of the present invention, the wet vulcanizing agent used in the wet vulcanization is at least one of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide. Specifically, the vulcanizing liquid used in the wet vulcanization includes the wet vulcanizing agent and an organic solvent. Preferably, the organic solvent is selected from at least one of cyclohexane, n-heptane, aviation kerosene and diesel. The mass fraction of the wet vulcanizing agent in the vulcanizing liquid is selected in a wide range, preferably 2%-7%, more preferably 4%-6%. The flow rate of the preferred vulcanizing liquid is 0.5-5mL·h -1 ·g -1 , preferably 1-4 mL·h -1 ·g -1 .

[0063] According to a preferred embodiment of the present invention, the amount of the metal salt of Group VIB and the metal salt of Group VIII is such that, in the prepared catalyst, the content of the metal sulfide of Group VIB calculated as sulfide is 10-30wt%, preferably 15-28wt%, and the content of the metal sulfide of Group VIII calculated as sulfide is 2-10wt%, preferably 4-8wt%, based on the total weight of the catalyst. Those skilled in the art can appropriately select the amount of the metal salt of Group VIB and the metal salt of Group VIII and the sulfurization conditions according to this requirement.

[0064] According to the present invention, preferably, the amount of the catalyst precursor and the molecular sieve is such that the content of the molecular sieve in the prepared catalyst is 1-20wt%, preferably 1-12wt%, and more preferably 1.5-8wt%, based on the total weight of the catalyst. The method provided by the present invention adds the molecular sieve to the catalyst, and the molecular sieve is loaded on the outer surface of the catalyst instead of being kneaded with the carrier, which is beneficial to increase the ratio of direct action of the molecular sieve and the active metal, and improve the hydrogenation activity of the catalyst; on the other hand, the hydrogenation saturation and ring-opening chain-breaking activity of polycyclic aromatic hydrocarbons can be accurately controlled by controlling the type and content of the molecular sieve, and the catalyst has high flexibility; the third aspect increases the utilization rate of the molecular sieve, thereby reducing the amount of the molecular sieve and reducing the cost of the catalyst.

[0065] According to the method provided by the present invention, the selection range of the molecular sieve type in step (3) can be the same as the selection range of the molecular sieve type in the hydrogenation catalyst described in the first aspect above, and the present invention will not be repeated here.

[0066] According to the method provided by the present invention, there is no particular limitation on the method of introducing the molecular sieve into the catalyst precursor in step (3), and the catalyst precursor and the molecular sieve may be directly mixed or the catalyst precursor and the molecular sieve precursor may be mixed and then subjected to hydrothermal treatment.

[0067] Preferably, the method of introducing the molecular sieve into the catalyst precursor in step (3) is carried out in at least one of the following ways:

[0068] (a) subjecting the catalyst precursor and the molecular sieve precursor to hydrothermal treatment, and performing the drying and calcining described in step (3) under an inert atmosphere;

[0069] (b) In the presence of a solvent, the catalyst precursor is mixed with the ball-milled molecular sieve, and then the mixture is dried and calcined as described in step (3).

[0070] According to the present invention, it is understood that the molecular sieve precursor can be a gel that generates the above-mentioned type of molecular sieve by hydrothermal treatment. Preferably, in mode (a), the molecular sieve precursor includes a gel formed by mixing a silicon source and / or an aluminum source, a precipitant, a template and water. Its preparation method is well known to those skilled in the art, and the molecular sieve can be formed by a precipitation method or a sol-gel method.

[0071] The types of the silicon source and / or aluminum source, precipitant, and template agent are well known to those skilled in the art. The silicon source is preferably selected from at least one of sodium silicate, tetraethyl orthosilicate, silica sol, and chromatography silica gel. The aluminum source is preferably selected from at least one of sodium aluminate, aluminum hydroxide, and pseudo-boehmite. The precipitant is preferably selected from at least one of sodium hydroxide, ammonia water, and potassium hydroxide. The template agent is preferably selected from at least one of hexadecyltrimethylammonium bromide, ethylenediamine, n-butylamine, tetrapropylammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, di-n-propylamine, diisopropylamine, and methylcellulose.

[0072] According to the present invention, when the molecular sieve is a silica-alumina molecular sieve, preferably, the molar composition of the gel is n(SiO2):n(Al2O3):n(Na2O):n(template):n(H2O)=(5-30):1:(1-10):(1-10):(100-300).

[0073] According to the present invention, when the molecular sieve is an all-silicon molecular sieve, preferably, the molar composition of the gel is n(SiO2):n(Na2O):n(template):n(H2O)=100:(10-30):(10-30):(1500-3000).

[0074] The present invention has a wide range of conditions for the hydrothermal treatment, based on the ability to obtain the molecular sieve. Preferably, the conditions for the hydrothermal treatment include: temperature of 90-200°C, pressure of 0.1-2MPa, pH of 7.5-9, and time of 5-48 hours.

[0075] According to the present invention, preferably, in mode (b), the particle size of the molecular sieve after ball milling is 0.1-10 nm, more preferably 0.1-5 nm. This preferred embodiment is more conducive to the role of the molecular sieve. The present invention has no particular limitation on the parameters and equipment of ball milling.

[0076] According to a preferred embodiment of the present invention, the drying conditions in step (3) include: a temperature of 20-90° C. and a time of 4-16 hours.

[0077] According to a preferred embodiment of the present invention, the calcination conditions in step (3) include: a temperature of 300-500° C. and a time of 2-5 hours.

[0078] The drying and calcining in step (3) can be carried out under an inert atmosphere. The specific selection of the inert atmosphere can be as described above.

[0079] The third aspect of the present invention provides the use of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in the hydrogenation of oil products.

[0080] The hydrogenation catalyst provided by the present invention can be used in different oil hydrogenation by matching different active metals and molecular sieve types, preferably in oil hydrogenation refining, oil hydrogenation upgrading, oil hydrogenation cracking or special oil hydrogenation refining, and more preferably in the hydrogenation saturation reaction of polycyclic aromatic hydrocarbons.

[0081] The catalyst provided by the invention has high activity and selectivity, and when applied to the polycyclic aromatic hydrocarbon hydrogenation saturation reaction process, it has high polycyclic aromatic hydrocarbon hydrogenation saturation activity and selectivity.

[0082] The fourth aspect of the present invention provides a method for hydrogenating an oil product, in particular a method for hydrogenating and saturating polycyclic aromatic hydrocarbons, comprising contacting the oil product with the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect.

[0083] Preferably, the oil product contains polycyclic aromatic hydrocarbons, and the hydrogenation reaction includes a polycyclic aromatic hydrocarbon hydrogenation saturation reaction. The content of polycyclic aromatic hydrocarbons in the oil product is preferably 5-70wt%.

[0084] The hydrogenation catalyst provided by the present invention is suitable for hydrogenation reaction of various oil products containing polycyclic aromatic hydrocarbons, including but not limited to diesel.

[0085] Preferably, the oil product contains 10-60wt% polycyclic aromatic hydrocarbons, 10-30wt% monocyclic aromatic hydrocarbons, and 10-80wt% alkanes. The oil product may also contain other elements, such as sulfur and nitrogen, and there is no particular limitation on their content.

[0086] Preferably, the reaction conditions include: a pressure of 1-12 MPa, more preferably 6-10 MPa, a hydrogen partial pressure of 50%-90% of the total pressure; an oil volume space velocity of 0.1-10 h -1 , more preferably 0.5-3h -1 The reaction temperature is 200-400°C, more preferably 330-380°C, and the volume ratio of hydrogen to oil is 10-1000:1, more preferably 100-800:1.

[0087] The following examples and comparative examples are used to further illustrate the catalyst and the preparation process and product performance of the method provided by the present invention, but the following examples do not constitute a limitation to the method of the present invention.

[0088] In the following examples and comparative hydrogenation catalysts, the proportion of the amount of molecular sieve directly interacting with the VIB group metal sulfide to the total amount of molecular sieve is characterized by TEM-EDS (transmission electron microscope-energy dispersive X-ray spectroscopy), and the specific method is described in the specific implementation section. The content of the VIB group metal sulfide and the VIII group metal sulfide can be obtained by joint characterization by inductively coupled plasma ICP and XPS energy spectrum, and the specific method is described in the specific implementation section.

[0089] Example 1

[0090] (1) An aqueous solution containing 50 wt% propylene glycol was impregnated into an alumina carrier, which was then dried at 80°C for 4 hours in a N2 atmosphere and calcined at 300°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0091] (2) The pretreated support prepared in step (1) was impregnated with a solution of nickel nitrate and ammonium heptamolybdate by pore saturation impregnation, and then dried at 90° C. for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol% H2S at a flow rate of 10 mL min -1 ·g -1 The sulfurization temperature is 290°C, the sulfurization pressure is 3.2MPa, the sulfurization time is 4h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0092] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 150°C, 1.0 MPa, pH=8.0 for 10 h; then filtered, washed three times with deionized water, dried at 90°C for 3 h in a nitrogen atmosphere, and calcined at 450°C for 3 h to obtain catalyst C-1.

[0093] The weight percentages of the components in catalyst C-1 are: MoS2 is 20%, NiS is 4.2%, Y molecular sieve is 4.0%, and the rest is alumina carrier.

[0094] The TEM image of catalyst C-1 is shown in Figure 1 As shown in the XRD Figure 2 As shown, from Figure 2 It can be seen that the method provided by the present invention forms a molecular sieve in the catalyst.

[0095] Example 2

[0096] (1) An aqueous solution containing 15 wt% glucose was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0097] (2) The pretreated support prepared in step (1) was impregnated with a solution of nickel nitrate and ammonium heptamolybdate by pore saturation impregnation, and then dried at 90° C. for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol% H2S at a flow rate of 10 mL min -1 ·g -1 The sulfurization temperature is 300°C, the sulfurization pressure is 3.2MPa, the sulfurization time is 4h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0098] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(n-butylamine):n(H2O)=20:1:7:6:200, and stirred to form a uniform sol, i.e., a precursor of the ZSM-5 molecular sieve, which is then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 120°C, 1.0 MPa, and pH=8.5 for 20 h; then filtered, washed three times with deionized water, dried at 90°C for 3 h in a nitrogen atmosphere, and calcined at 450°C for 3 h to obtain catalyst C-2.

[0099] The weight percentages of the components in catalyst C-2 are: MoS2 is 21%, NiS is 4.2%, ZSM-5 molecular sieve is 3.5%, and the rest is alumina carrier.

[0100] Example 3

[0101] (1) An aqueous solution containing 50 wt% ethylene glycol was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 300°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0102] (2) The pretreated support prepared in step (1) was impregnated with a solution of nickel nitrate and ammonium heptamolybdate by pore saturation impregnation, and then dried at 90° C. for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol% H2S at a flow rate of 10 mL min -1 ·g -1 The sulfurization temperature is 290°C, the sulfurization pressure is 3.0MPa, the sulfurization time is 4h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0103] (3) Dissolve sodium aluminate and sodium hydroxide in deionized water, then add tetraethylammonium bromide, stir vigorously, slowly add silica sol, and age for 3 hours, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(tetraethylammonium bromide):n(H2O)=25:1:6:5:250, to form a precursor of β-type molecular sieve, and then mix it with the catalyst precursor prepared in step (2), and then hydrothermally treat it at 130°C, 1.0 MPa, pH=8.5 for 15 hours; then filter, wash three times with deionized water, dry at 90°C in a nitrogen atmosphere for 3 hours, and calcine at 450°C for 3 hours to obtain catalyst C-3.

[0104] The weight percentages of the components in catalyst C-3 are: MoS2 is 24%, NiS is 3.2%, β-type molecular sieve is 5.0%, and the rest is alumina carrier.

[0105] Example 4

[0106] (1) An aqueous solution containing 50 wt% ethylene glycol was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 250°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0107] (2) The pretreated support prepared in step (1) was impregnated with a solution of nickel nitrate and ammonium heptamolybdate by pore saturation impregnation, and then dried at 90° C. for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol% H2S at a flow rate of 10 mL min -1 ·g-1 The sulfurization temperature is 300°C, the sulfurization pressure is 3.0 MPa, the sulfurization time is 4 h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0108] (3) Hexadecyltrimethylammonium bromide and sodium hydroxide are mixed and then added to deionized water. After stirring, ethyl orthosilicate is added dropwise to the mixed solution. After stirring for 30 minutes, the molar ratio of each component is n(SiO2):n(Na2O):n(hexadecyltrimethylammonium bromide):n(H2O)=11:2:2:200 to form an MCM-41 molecular sieve precursor, which is then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 130°C, 1.0 MPa, and pH=8.5 for 15 hours; then filtered, washed with deionized water three times, dried at 80°C for 3 hours in a nitrogen atmosphere, and calcined at 500°C for 3 hours to obtain catalyst C-4.

[0109] The weight percentages of the components in catalyst C-4 are: MoS2 is 22%, NiS is 4.8%, MCM-41 molecular sieve is 3.8%, and the rest is alumina carrier.

[0110] Example 5

[0111] (1) A solution containing 100 wt% jet fuel (atmospheric distillation fraction with a distillation range of 100-220°C) was impregnated into an alumina carrier, which was then dried at 80°C for 4 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0112] (2) The pretreated support prepared in step (1) was impregnated with a solution of cobalt nitrate and ammonium heptamolybdate by pore saturation impregnation, and then dried at 90° C. for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol. % H2S at a flow rate of 10 mL min -1 ·g -1 The sulfurization temperature is 300°C, the sulfurization pressure is 3.2MPa, the sulfurization time is 4h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0113] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 150°C, 1.0 MPa, pH=9.0 for 15 h; then filtered, washed three times with deionized water, dried at 80°C for 3 h in a nitrogen atmosphere, and calcined at 450°C for 3 h to obtain catalyst C-5.

[0114] The weight percentages of the components in catalyst C-5 are: 20% MoS2, 5.0% CoS, 5.0% Y molecular sieve, and the rest is alumina carrier.

[0115] Example 6

[0116] (1) An aqueous solution containing 30 wt% glucose was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 350°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0117] (2) The pretreated support prepared in step (1) was impregnated with a solution of nickel nitrate and ammonium metatungstate by pore saturation impregnation, and then dried at 80°C for 3 h in a nitrogen atmosphere, and then subjected to a sulfidation treatment using hydrogen containing 1.5% by volume of H2S at a sulfidation temperature of 300°C and a hydrogen flow rate of 10 mL min -1 ·g -1 The sulfurization pressure was 3.0 MPa and the sulfurization time was 4 h, and then the temperature was cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0118] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(n-butylamine):n(H2O)=20:1:7:6:200, and stirred to form a uniform sol, i.e., a precursor of the ZSM-5 molecular sieve, which is then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 130°C, 1.0 MPa, and pH=8.5 for 15 h; then filtered, washed three times with deionized water, dried at 80°C for 3 h in a nitrogen atmosphere, and calcined at 450°C for 3 h to obtain catalyst C-6.

[0119] The weight percentages of the components in catalyst C-6 are: WS2 is 24%, NiS is 4.8%, ZSM-5 molecular sieve is 4.3%, and the rest is alumina carrier.

[0120] Example 7

[0121] (1) An aqueous solution containing 30 wt% glucose was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 300°C for 3 hours to obtain a pretreated carrier. The carbon content in the pretreated carrier is shown in Table 1.

[0122] (2) The pretreated support prepared in step (1) was impregnated with a solution of cobalt nitrate and ammonium metatungstate by pore saturation impregnation, and then dried at 90°C for 3 h in a nitrogen atmosphere, and then sulfided with hydrogen containing 1.5 vol% H2S at a flow rate of 10 mL min -1 ·g-1 The sulfurization temperature is 320°C, the sulfurization pressure is 3.0 MPa, the sulfurization time is 4 h, and then it is cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0123] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 130°C, 1.0 MPa, pH=8.5 for 15 h; then filtered, washed three times with deionized water, dried at 90°C for 3 h in a nitrogen atmosphere, and calcined at 450°C for 3 h to obtain catalyst C-7.

[0124] The weight percentages of the components in catalyst C-7 are: WS2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.

[0125] Example 8

[0126] Catalyst C-8 was obtained by following the method of Example 1, except that the alumina carrier was replaced by zirconium oxide.

[0127] Example 9

[0128] According to the method of Example 1, the difference is that in step (3), the catalyst precursor prepared in step (2) is directly mixed with the ball-milled Y-type molecular sieve (particle size is 0.2-2.0nm), and then the drying and calcination are performed. The preparation of the Y-type molecular sieve includes: adding sodium hydroxide, silica sol, sodium aluminate and ethylenediamine to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, stirring until a uniform sol is formed, and then hydrothermally treating at 150°C, 1.0MPa, pH=8.0 for 10h; then filtering, washing with deionized water three times, and then drying at 90°C for 3h in a nitrogen atmosphere, and calcining at 450°C for 3h to obtain catalyst C-9.

[0129] Example 10

[0130] Catalyst C-10 was obtained by following the method of Example 1, except that the content of molecular sieve was 16%, the content of MoS2 and NiS remained unchanged, and the content of alumina carrier was reduced accordingly.

[0131] Comparative Example 1

[0132] (1) Mix Y-type molecular sieve with alumina powder, nitric acid, starch and deionized water, wherein the mass ratio of Y-type molecular sieve: alumina powder: nitric acid: starch: deionized water is 8:92:4:3:60, and then knead and extrude into strips, and then dry at 80°C for 10 hours and calcine at 650°C for 3 hours to obtain a modified alumina carrier, in which the content of Y-type molecular sieve is 8%.

[0133] (2) The modified alumina carrier prepared in step (1) was impregnated with a mixed solution of phosphomolybdic acid and nickel nitrate, and then dried at 90°C for 3 hours, calcined at 450°C for 3 hours, and then subjected to a sulfurization treatment at a temperature of 320°C, a pressure of 3.0 MPa, and a time of 4 hours, and then cooled to room temperature in a N2 atmosphere to obtain a catalyst DC-1.

[0134] The weight percentages of the components in the catalyst DC-1 are: MoS2 is 20%, NiS is 4.8%, the Y molecular sieve content is 6%, and the rest is alumina.

[0135] Comparative Example 2

[0136] (1) A solution of cobalt nitrate and ammonium metatungstate was impregnated into an alumina carrier, and then dried at 90°C for 3 h in a nitrogen atmosphere. The carrier was then sulfided with hydrogen containing 1.5 vol% H2S at a temperature of 320°C and a pressure of 3.0 MPa for 4 h. The carrier was then cooled to room temperature in a N2 atmosphere to obtain a catalyst precursor.

[0137] (2) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, which is then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated at 130°C, 1.0 MPa, and pH=8.5 for 15 h; then filtered, washed three times with deionized water, and dried at 90°C in a nitrogen atmosphere for 3 h to obtain catalyst DC-2.

[0138] The weight percentages of the components in the catalyst DC-2 are: WS2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.

[0139] Comparative Example 3

[0140] (1) A solution containing 30 wt% glucose was impregnated into an alumina carrier, which was then dried at 90°C for 4 hours in a N2 atmosphere and calcined at 300°C for 3 hours to obtain a pretreated carrier.

[0141] (2) impregnating the pretreated support prepared in step (1) with a solution of cobalt nitrate and ammonium metatungstate, and then drying at 80° C. for 3 h in a nitrogen atmosphere and calcining at 400° C. for 3 h to obtain a catalyst precursor.

[0142] (3) Sodium hydroxide, silica sol, sodium aluminate and ethylenediamine are added to deionized water, wherein the molar ratio of each component is n(SiO2):n(Al2O3):n(Na2O):n(ethylenediamine):n(H2O)=12:1:6:3:180, and stirred to form a uniform sol, i.e., a precursor of Y molecular sieve, and then mixed with the catalyst precursor prepared in step (2), and then hydrothermally treated for 15 h at 130°C, 1.0 MPa, and pH=8.5; then filtered, washed three times with deionized water, dried at 90°C for 3 h in a nitrogen atmosphere, calcined at 450°C for 3 h, and then sulfurized with hydrogen containing 1.5 volume % H2S, the sulfurization temperature is 320°C, the sulfurization pressure is 3.0 MPa, and the sulfurization time is 4 h, and then cooled to room temperature in a N2 atmosphere to obtain catalyst DC-3.

[0143] The weight percentages of the components in the catalyst DC-3 are: WS2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.

[0144] In the above embodiments and comparative examples, the proportion of the amount of molecular sieve directly reacting with the VIB group metal sulfide to the total amount of molecular sieve, calculated as silicon element, is listed in Table 1.

[0145] Table 1

[0146]

[0147]

[0148] Application Example 1

[0149] This application example illustrates the hydrogenation performance of the catalyst provided by the present invention for diesel polycyclic aromatic hydrocarbons.

[0150] The raw oil used for evaluation is a diesel raw material provided by a refinery of Sinopec, and its main properties are as follows: distillation range 200-380°C, sulfur content of 1.5wt%, nitrogen content of 580μg / g, monocyclic aromatic hydrocarbon content of 20wt%, and polycyclic aromatic hydrocarbon content of 26wt%. A 200mL fixed bed hydrogenation device was used to evaluate the hydrogenation reaction performance of the catalysts provided in the embodiment and the comparative example. The evaluation reaction conditions are: operating pressure 6.4MPa, reaction temperature 370°C, hydrogen / oil volume ratio 600:1, volume space velocity 1.2h -1 The evaluation results of reaction time of 100 h are shown in Table 2.

[0151] Table 2

[0152]

[0153] Application Example 2

[0154] This application example illustrates the performance of the catalyst provided by the present invention in catalyzing the hydrogenation of polycyclic aromatic hydrocarbons in diesel.

[0155] The raw oil used for evaluation is catalytic diesel provided by a refinery of Sinopec, and its main properties are as follows: distillation range 200-380°C, sulfur content of 2.5wt%, nitrogen content of 1050μg / g, monocyclic aromatic hydrocarbon content of 20wt%, and polycyclic aromatic hydrocarbon content of 55wt%. A 200mL fixed bed hydrogenation device was used to evaluate the hydrogenation reaction performance of the catalysts provided in Examples 2, 3, and 4. The evaluation reaction conditions are: operating pressure 8.4MPa, reaction temperature 360°C, hydrogen / oil volume ratio 800:1, and volume space velocity 1.0h -1 The evaluation results of reaction time 100 h are shown in Table 3.

[0156] Table 3

[0157]

Claims

1. A hydrogenation catalyst, characterized in that The hydrogenation catalyst is a sulfided hydrogenation catalyst, comprising a carrier, a molecular sieve and an active component, wherein the active component comprises at least one of the metal elements of Group VIII and at least one of the metal elements of Group VIB. The hydrogenation catalyst is characterized by a TEM-EDS method, and the proportion of the molecular sieve directly reacting with the metal sulfide of Group VIB to the total amount of the molecular sieve is 60-100% based on silicon element.

2. The catalyst according to claim 1, wherein Calculated on the basis of silicon element, the amount of molecular sieve directly interacting with the VIB group metal sulfide accounts for 65%-95% of the total amount of molecular sieve.

3. The catalyst according to claim 2, wherein Calculated on the basis of silicon element, the amount of molecular sieve directly interacting with the VIB group metal sulfide accounts for 70%-90% of the total amount of molecular sieve.

4. The catalyst according to claim 3, wherein Calculated on the basis of silicon element, the amount of molecular sieve directly interacting with the VIB group metal sulfide accounts for 80%-90% of the total amount of molecular sieve.

5. The catalyst according to claim 1, wherein Based on the total weight of the catalyst, the content of the molecular sieve is 1-20wt%.

6. The catalyst according to claim 5, wherein Based on the total weight of the catalyst, the content of the molecular sieve is 1-12 wt%.

7. The catalyst according to claim 6, wherein Based on the total weight of the catalyst, the content of the molecular sieve is 1.5-8wt%.

8. The catalyst according to claim 1, wherein Based on the total weight of the catalyst, the content of the VIB group metal sulfide as sulfide is 10-30 wt %; the content of the VIII group metal sulfide as sulfide is 2-10 wt %.

9. The catalyst according to claim 8, wherein Based on the total weight of the catalyst, the content of the VIB group metal sulfide as sulfide is 15-28 wt %; the content of the VIII group metal sulfide as sulfide is 4-8 wt %.

10. The catalyst according to any one of claims 1 to 9, wherein The metal elements of Group VIB are Mo and / or W, and the metal elements of Group VIII are Co and / or Ni.

11. The catalyst according to any one of claims 1 to 9, wherein The molecular sieve is at least one selected from Y-type molecular sieve, ZSM-5 molecular sieve, β-type molecular sieve and MCM-41 molecular sieve.

12. The catalyst according to any one of claims 1 to 9, wherein The carrier is selected from at least one of aluminum oxide, silicon oxide, titanium oxide and zirconium oxide.

13. The catalyst according to claim 12, wherein The carrier is alumina.

14. A method for preparing the hydrogenation catalyst according to any one of claims 1 to 13, characterized in that: The method comprises the following steps: (1) impregnating a carrier with a solution containing an organic additive, drying and calcining under an inert atmosphere to obtain a pretreated carrier; (2) introducing a Group VIB metal salt and a Group VIII metal salt into the pretreated support by an impregnation method, and then sulfiding the pretreated support to obtain a catalyst precursor; (3) Introducing molecular sieves into the catalyst precursor, followed by drying and calcining.

15. The preparation method according to claim 14, wherein: The carbon content in the pretreated carrier is 3-20wt%.

16. The preparation method according to claim 15, wherein: The carbon content in the pretreated carrier is 5-10 wt %.

17. The preparation method according to claim 14, wherein: The carbon number of the organic auxiliary agent in step (1) is 2-10, and the organic auxiliary agent contains hydroxyl and / or carboxyl groups.

18. The preparation method according to claim 17, wherein: The organic auxiliary agent is selected from at least one of ethylene glycol, glycerol, butylene glycol, pentanediol, acetic acid, citric acid, glucose, malonic acid, succinic acid and glutaric acid.

19. The preparation method according to claim 14, wherein: The carrier is selected from at least one of aluminum oxide, silicon oxide, titanium oxide and zirconium oxide.

20. The preparation method according to claim 19, wherein: The carrier is alumina.

21. The preparation method according to claim 14, wherein: The metals of Group VIB are Mo and / or W, and the metals of Group VIII are Co and / or Ni.

22. The preparation method according to claim 14, wherein: The amounts of the VIB group metal salt and the VIII group metal salt used are such that in the prepared catalyst, based on the total weight of the catalyst, the content of the VIB group metal sulfide as sulfide is 10-30 wt%; and the content of the VIII group metal sulfide as sulfide is 2-10 wt%.

23. The preparation method according to claim 22, wherein: The amounts of the Group VIB metal salt and the Group VIII metal salt are such that in the prepared catalyst, based on the total weight of the catalyst, the content of the Group VIB metal sulfide as sulfide is 15-28 wt%; and the content of the Group VIII metal sulfide as sulfide is 4-8 wt%.

24. The preparation method according to any one of claims 14 to 23, wherein: The vulcanization in step (2) is dry vulcanization or wet vulcanization.

25. The preparation method according to claim 24, wherein: The dry vulcanizing agent used in the dry vulcanization is hydrogen sulfide, and the wet vulcanizing agent used in the wet vulcanization is at least one of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide.

26. The preparation method according to any one of claims 14 to 23, wherein: The vulcanization conditions in step (2) include: a vulcanization pressure of 3.2-6.4 MPa, a vulcanization temperature of 250-400°C, a vulcanization time of 4-12 h, and a hydrogen flow rate of 2-25 mL·min -1 ·g -1 .

27. The preparation method according to any one of claims 14 to 23, wherein: The catalyst precursor and the molecular sieve are used in such an amount that the content of the molecular sieve in the prepared catalyst is 1-20 wt % based on the total weight of the catalyst.

28. The preparation method according to claim 27, wherein The catalyst precursor and the molecular sieve are used in such an amount that the content of the molecular sieve in the prepared catalyst is 1-12 wt % based on the total weight of the catalyst.

29. The preparation method according to claim 28, wherein The catalyst precursor and the molecular sieve are used in such an amount that the content of the molecular sieve in the prepared catalyst is 1.5-8 wt % based on the total weight of the catalyst.

30. The preparation method according to any one of claims 14 to 23, wherein: The molecular sieve is at least one selected from Y-type molecular sieve, ZSM-5 molecular sieve, β-type molecular sieve and MCM-41 molecular sieve.

31. The preparation method according to any one of claims 14 to 23, wherein: The method of introducing the molecular sieve into the catalyst precursor in step (3) is carried out in at least one of the following ways: (a) subjecting the catalyst precursor and the molecular sieve precursor to hydrothermal treatment, and performing the drying and calcining described in step (3) under an inert atmosphere; (b) In the presence of a solvent, the catalyst precursor is mixed with the ball-milled molecular sieve, and then the mixture is dried and calcined as described in step (3).

32. The preparation method according to claim 31, wherein In mode (a), the molecular sieve precursor comprises a gel formed by mixing a silicon source and / or an aluminum source, a precipitant, a template and water.

33. The preparation method according to claim 31, wherein The conditions of the hydrothermal treatment include: temperature of 90-200° C., pressure of 0.1-2 MPa, pH of 7.5-9, and time of 5-48 hours.

34. The preparation method according to claim 31, wherein In the method (b), the particle size of the molecular sieve after ball milling is 0.1-10 nm.

35. The preparation method according to claim 34, wherein: In the method (b), the particle size of the molecular sieve after ball milling is 0.1-5 nm.

36. Use of the hydrogenation catalyst described in any one of claims 1 to 13 or the hydrogenation catalyst prepared by any one of the preparation methods of claims 14 to 35 in the hydrogenation of oil products.

37. Use of the hydrogenation catalyst described in any one of claims 1 to 13 or the hydrogenation catalyst prepared by the preparation method of any one of claims 14 to 35 in oil hydrorefining, oil hydroupgrading, hydrocracking or special oil hydrorefining.

38. Use of the hydrogenation catalyst described in any one of claims 1 to 13 or the hydrogenation catalyst prepared by the preparation method described in any one of claims 14 to 35 in the hydrogenation saturation reaction of polycyclic aromatic hydrocarbons.

39. A method for hydrogenating an oil product, comprising contacting the oil product with the hydrogenation catalyst described in any one of claims 1 to 13 or the hydrogenation catalyst prepared by any one of the preparation methods of claims 14 to 35.

40. The method of claim 39, wherein: The oil product contains polycyclic aromatic hydrocarbons, and the hydrogenation reaction includes a polycyclic aromatic hydrocarbon hydrogenation saturation reaction.

41. The method of claim 39, wherein: The reaction conditions include: pressure of 1-12MPa, hydrogen partial pressure of 50%-90% of total pressure, oil volume space velocity of 0.1-10h -1 , the reaction temperature is 200-400℃, and the volume ratio of hydrogen to oil is 10-1000:1.

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