WO2023072117A1 - 加氢催化剂及其制备方法和应用，油品加氢反应方法 - Google Patents

加氢催化剂及其制备方法和应用，油品加氢反应方法 Download PDF

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WO2023072117A1
WO2023072117A1 PCT/CN2022/127557 CN2022127557W WO2023072117A1 WO 2023072117 A1 WO2023072117 A1 WO 2023072117A1 CN 2022127557 W CN2022127557 W CN 2022127557W WO 2023072117 A1 WO2023072117 A1 WO 2023072117A1
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Prior art keywords
catalyst
molecular sieve
hydrogenation
carrier
molecular sieves
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PCT/CN2022/127557
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English (en)
French (fr)
Inventor
刘丽
杨成敏
郑步梅
郭蓉
段为宇
姚运海
陈晓贞
孙进
尹晓莹
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CA3236627A priority Critical patent/CA3236627C/en
Priority to KR1020247018288A priority patent/KR20240095335A/ko
Priority to US18/705,928 priority patent/US20250319460A1/en
Priority to CN202280070396.XA priority patent/CN118119449B/zh
Priority to EP22885994.8A priority patent/EP4410424A4/en
Publication of WO2023072117A1 publication Critical patent/WO2023072117A1/zh
Anticipated expiration legal-status Critical
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the field of hydrogenation of oil products, and relates to a hydrogenation catalyst, a preparation method and application thereof, and a method for hydrogenation reaction of oil products.
  • CN200810104303.2 discloses a modified molecular sieve-based precious metal diesel oil deep hydrogenation dearomatization catalyst and its preparation method, which is suitable for FCC diesel oil hydrogenation dearomatization process, especially suitable for deep hydrogenation of diesel oil after FCC diesel oil hydrogenation and upgrading Dearomatization, the dearomatized diesel oil can be used as a blending component of high-quality diesel oil.
  • the catalyst is composed of modified HY molecular sieve as carrier and active components such as noble metals such as 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 such as Cr, Zn, Sn, Mo, etc.
  • the catalyst has the characteristics of inhibiting deep cracking and selective ring-opening performance, and the catalyst can be used for deep dearomatization reaction in the second stage of two-stage hydrogenation upgrading of diesel oil. It can be used for deep dearomatization of diesel oil, but the carrier of the catalyst is a high-priced and high-content molecular sieve, and the active metal is a high-priced noble metal, which is too expensive. At the same time, the high-content molecular sieve carrier, most of which have no effect.
  • CN201210332369.3 discloses a method for hydrogenation conversion of polycyclic aromatic hydrocarbons, including: (1) in at least one hydrogenation reaction zone, in the presence of hydrogen, the raw material containing polycyclic aromatic hydrocarbons is contacted with a hydrogenation catalyst to obtain a A reaction product in which polycyclic aromatic hydrocarbons are at least partially hydrogenated; (2) in at least one hydrocracking reaction zone, the polycyclic aromatic hydrocarbons obtained in step (1) are at least partially hydrogenated in the presence of hydrogen The reaction product is contacted with a hydrocracking catalyst; wherein, the hydrogenation catalyst in the hydrogenation reaction zone and the selection of operating conditions make the conversion rate of polycyclic aromatic hydrocarbons in the raw material containing polycyclic aromatic hydrocarbons more than 40% by weight.
  • the relative yield of the monocyclic hydrogenation product is 4-80%; the hydrocracking catalyst in the hydrocracking reaction zone and the selection of operating conditions make the total amount of polycyclic aromatic hydrocarbons in the raw material containing polycyclic aromatic hydrocarbons as a benchmark
  • the conversion rate of 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 the hydroconversion of polycyclic aromatic hydrocarbons adopts two kinds of catalysts for grading, and the molecular sieve in the carrier of the hydrocracking catalyst is added to the carrier by a mixing method, and most of the molecular sieves are wrapped by alumina, which does not work. Thus affecting the performance of the hydrocracking catalyst.
  • the invention provides a hydrogenation catalyst, its preparation method and application, and a method for hydrogenation reaction of oil products.
  • the hydrogenation catalyst provided by the invention has high activity and selectivity, and can control polycyclic aromatic hydrocarbons to open rings and chains, and generate single-ring aromatic hydrocarbons with long chain branches, which can be used as raw materials for ethylene cracking and high-quality diesel oil product.
  • the first aspect of the present invention provides a hydrogenation catalyst
  • the hydrogenation catalyst is a sulfided hydrogenation catalyst, including a carrier, a molecular sieve and an active component
  • the active component includes at least one of Group VIII metal elements and At least one of the Group VIB metal elements
  • the hydrogenation catalyst is characterized by the TEM-EDS method, and the amount of the molecular sieve directly interacting with the Group VIB metal sulfide accounts for 60-100% of the total amount of the molecular sieve in terms of silicon element %.
  • the molecular sieve content is 1-20 wt%, preferably 1-12 wt%, more preferably 1.5-8 wt%.
  • a second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the following steps:
  • the third aspect of the present invention provides the application of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in oil hydrogenation.
  • the fourth aspect of the present invention provides a method for hydrogenation reaction of oil, comprising contacting the oil with the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect.
  • the oil contains polycyclic aromatic hydrocarbons
  • the hydrogenation reaction includes a hydrogenation saturation reaction of polycyclic aromatic hydrocarbons.
  • the catalyst of the present invention includes a carrier, a molecular sieve and an active component, and more molecular sieves directly act on the active metal, so the utilization rate of the molecular sieve and the active metal is higher, and the activity effect is better, and it is beneficial to reduce the molecular sieve. dosage, reducing the cost of the catalyst.
  • the preparation method provided by the present invention prepares the catalyst through the sequence of carrier pretreatment-loading active metal-sulfurization-loading molecular sieve, so that more molecular sieves can directly act on the active metal, and better play an active role.
  • the preparation method provided by the present invention is directly vulcanized after impregnating the active metal and drying, without the roasting process, which not only reduces the interaction between the metal oxide and the carrier, but also simplifies the process.
  • Fig. 1 is the high-resolution transmission electron microscope figure of the catalyst that the embodiment of the present invention 1 makes;
  • Fig. 2 is the X-ray diffraction energy spectrum of the catalyst prepared in Example 1 of the present invention.
  • the first aspect of the present invention provides a hydrogenation catalyst
  • the hydrogenation catalyst is a sulfided hydrogenation catalyst, including a carrier, a molecular sieve and an active component
  • the active component includes at least one of Group VIII metal elements and At least one of the Group VIB metal elements
  • the hydrogenation catalyst is characterized by the TEM-EDS method, and the amount of the molecular sieve directly interacting with the Group VIB metal sulfide accounts for 60-100% of the total amount of the molecular sieve in terms of silicon element %, preferably 65%-95%, more preferably 70%-90%, most preferably 80%-90%.
  • the ratio of the amount of molecular sieves directly interacting with Group VIB metal sulfides to the total amount of molecular sieves is significantly higher than that of the catalysts provided in the prior art, and the utilization rate of molecular sieves and active metals is higher, and better performance activity, and is beneficial to reduce the amount of molecular sieves and reduce the cost of the catalyst.
  • the direct interaction of the molecular sieve with the Group VIB metal sulfide refers to the fact that the molecular sieve is supported on the wafer surface of the Group VIB metal sulfide.
  • the total amount of molecular sieves (in terms of silicon) represents the total content of molecular sieves in the catalyst, and the molecular sieves directly interact with VIB group
  • the amount of metal sulfide action refers to the content of molecular sieves within 2nm from the outermost layer of the Group VIB metal sulfide wafer (calculated as silicon element).
  • the ratio of the amount of molecular sieves directly interacting with Group VIB metal sulfides to the total amount of molecular sieves was characterized by TEM-EDS (Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy) method. Equipped with scanning transmission accessories and X-ray energy spectrum accessories of American EDAX company. Electron microscope acceleration voltage is 200KV, in STEM mode, condenser aperture is set to 2, and Spot size is set to 0.5nm.
  • the measurement process is as follows: Grind the catalyst particles, use the suspension method to prepare samples, put 0.1g of the catalyst sample into a 2mL container, disperse it ultrasonically with absolute ethanol, take the supernatant, take two to three drops with a dropper, and drop it on a diameter of On a 3mm sample net, the sample to be tested is obtained by drying, and then the sample to be tested is observed and analyzed by TEM, and then combined with EDS to observe the active phase (Group VIB metal sulfide wafer, as shown in Figure 1) and the distance from the edge endpoint is less than 2nm
  • Statistical analysis is carried out on the Si content at the site, and the proportion of the amount of molecular sieves directly interacting with Group VIB metal sulfides to the total amount of molecular sieves is obtained based on the corresponding peak area of Si.
  • the present invention has a wide range of options for the type and content of molecular sieves in the catalyst, and can be properly selected according to different hydrogenation reactions. Different hydrogenation purposes can be achieved by controlling the type and content of molecular sieves, for example, by controlling the molecular sieves.
  • the type and content can precisely control the hydrogenation saturation and ring-opening and chain-breaking activity of polycyclic aromatic hydrocarbons, and the catalyst has high flexibility.
  • the molecular sieve content is 1-20wt%, preferably 1-12wt%, more preferably 1.5-8wt%, most preferably 2-6wt%.
  • the present invention improves the utilization rate of the molecular sieve by increasing the ratio of the amount of the molecular sieve that directly interacts with the VIB group metal sulfide to the total amount of the molecular sieve, and even at a lower content of the molecular sieve, the catalyst can exert better hydrogenation performance, which is beneficial Reduce catalyst costs.
  • the method for determining the content of the molecular sieve in the catalyst is not particularly limited in the present invention. It can be determined by combining the amount of silicon oxide with the crystal form of the molecular sieve measured by XRD, or can be calculated by feeding the catalyst during the preparation process.
  • the content of the Group VIB metal sulfide in terms of sulfide is 10-30wt%, preferably 15-28wt%, such as 15wt%, 17wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, and any value in the range formed by any two of these values;
  • the content of Group VIII metal sulfide is 2-10wt% in terms of sulfide, Preferably 4-8wt%, such as 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, and any value in the range formed by any two of these values.
  • the hydrogenation catalyst provided by the invention is a hydrogenation catalyst in a sulfided state, and most active components exist in the form of sulfides.
  • the catalyst provided by the present invention does not exclude the inclusion of a small amount of Group VIB metal oxides and Group VIII metal oxides.
  • the hydrogenation catalyst provided by the present invention may also contain other components. It can be known that the sum of the contents of all components in the hydrogenation catalyst is 100%.
  • the Group VIB metal element is Mo and/or W
  • the Group VIII metal element is Co and/or Ni.
  • the Group VIB metal sulfides may refer to MoS 2 and WS 2
  • the Group VIII metal sulfides may refer to CoS and NiS.
  • the contents of Group VIB metal sulfides and Group VIII metal sulfides can be jointly characterized by inductively coupled plasma ICP and XPS energy spectroscopy.
  • the total amount of Group VIB metals in the catalyst is firstly characterized by ICP. content and the total content of Group VIII metals, and then quantitatively characterize the content of metal elements in different valence states in the catalyst by XPS energy spectrometer.
  • the measurement conditions of the XPS energy spectrum include: the vacuum degree of the analysis room is ⁇ 5 ⁇ 10 -10 mbar; the vacuum degree of the preparation room is ⁇ 1 ⁇ 10 -7 mbar; the sensitivity of the double anode is 4.5 ⁇ 10 6 , and the energy resolution is 1.0eV; The sensitivity is 1.4 ⁇ 10 5 , and the energy resolution is 0.5eV.
  • XPSPEAK Version 4.0 was used to fit and split the energy spectra of Mo3d, W4f, Co2p, and Ni2p respectively, and the contents of metal elements in different valence states in the catalyst were calculated according to the peak areas.
  • the molecular sieve is selected from at least one of Y-type molecular sieves, ZSM-5 molecular sieves, ⁇ -type molecular sieves and MCM-41 molecular sieves.
  • the molecular sieve can be obtained commercially or synthesized by existing methods, which is not particularly limited in the present invention.
  • the present invention has no particular limitation on the carrier, it can be various carriers conventionally used in the art, it can be a commercially available commodity, and it can also be prepared by any method in the prior art.
  • the carrier can be an inorganic refractory oxidation-resistant thing.
  • the carrier is selected from at least one of alumina, silica, titania and zirconia. Taking cost and effect into consideration, it is preferable that the carrier is alumina.
  • the carrier may also contain doping elements, such as one or more of phosphorus, silicon, boron, fluorine, sodium and other elements.
  • the addition amount of the doping element can be a conventional addition amount, preferably accounting for 0.5%-6% of the mass of the carrier.
  • a second aspect of the present invention provides a method for preparing a hydrogenation catalyst, the method comprising the following steps:
  • an inert surface layer of C is formed on the surface of the carrier.
  • the interaction between the metal and the carrier can be weakened; Layer, C layer is non-polar, molecular sieve will interact with metal more, increase the proportion of molecular sieve and active metal directly.
  • the carbon content in the pretreated carrier is 3-20wt%, preferably 5-10wt%. Adopting this preferred embodiment can not only increase the proportion of molecular sieves directly interacting with active metals, but also ensure the stability of the catalyst.
  • the present invention has no special limitation on the type of the organic auxiliary agent, as long as it can be dried and calcined under an inert atmosphere to form a C inert surface layer on the surface of the carrier.
  • the organic auxiliary agent is selected from hydrocarbons, alcohols, carboxylic acid Classes, more preferably can be selected from ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, glucose, malonic acid, succinic acid, glutaric acid, jet fuel and C9 aromatics at least A sort of.
  • the number of carbon atoms of the organic additive is preferably 2-10.
  • the organic auxiliary agent contains hydroxyl and/or carboxyl groups, and this preferred embodiment is more conducive to the dispersion of active metals.
  • the organic auxiliary agent is selected from the group consisting of ethylene glycol, glycerol, butanediol, pentanediol, acetic acid, citric acid, glucose, malonic acid, succinic acid and pentadiol at least one of the acids.
  • the solution containing the organic auxiliary agent may also optionally contain a solvent.
  • step (1) only needs to form a C inert surface layer on the surface of the carrier.
  • the solution of the organic auxiliary agent can be impregnated onto the carrier, when the organic auxiliary agent is a solid organic auxiliary agent, it is preferred that the solution containing the organic auxiliary agent also contains a solvent.
  • the organic auxiliary agent When it is a liquid, the solution containing the organic auxiliary agent may or may not contain a solvent.
  • the range of solvents in the solution containing the organic auxiliary agent is wide, and there is no special limitation, as long as the organic auxiliary agent can be dissolved (such as water or ethanol), those skilled in the art can select according to the specific organic auxiliary agent. Proper selection of additives.
  • the content of the organic auxiliary agent is 10-30 wt%.
  • the content of the organic auxiliary agent is 50-100 wt%.
  • the amount of the solution containing the organic auxiliary agent can be determined according to the saturated impregnation of the pores.
  • 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.
  • the drying conditions in the step (1) of the present invention preferably include: a temperature of 20-90° C. and a time of 4-16 hours.
  • the roasting conditions in the step (1) of the present invention preferably include: the temperature is 200-400° C., and the time is 3-8 hours; preferably, the temperature is 250-350° C., and the time is 3-5 hours.
  • the selection range of the carrier and the metals of the Group VIB and the metals of the Group VIII can be compared with that of the metal of the carrier, the metals of the Group VIB and the metals of the Group VIII in the hydrogenation catalyst described in the first aspect above.
  • the selection range is the same, and the present invention will not repeat them here.
  • the impregnation method in step (2) is not particularly limited, and may be equal-volume impregnation or supersaturated impregnation.
  • the Group VIB metal salt and the Group VIII metal salt can be introduced into the pretreated carrier simultaneously through co-impregnation, or can be introduced into the pretreated carrier separately through step-by-step impregnation, and there is no special limitation on the order of introduction of the two.
  • the Group VIB metal salt and the Group VIII metal salt are simultaneously introduced into the pretreated support by co-impregnation.
  • step (2) includes: impregnating the pretreated carrier with an impregnating solution containing metal salts of Group VIB and metal salts of Group VIII, and then drying.
  • the preparation method of the dipping 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 may be the same as above, and will not be repeated here.
  • the drying conditions include: the temperature is 20-90° C., and the time is 4-16 hours.
  • the types of metal salts of Group VIB and metal salts of Group VIII are selected from a wide range, based on the subsequent transformation into respective metal sulfides, preferably, the metal salts of Group VIB are Group VIB Phosphate and/or ammonium salts of metals, the metal salt of Group VIII is at least one of nitrates, acetates and sulfates of metals of Group VIII.
  • the present invention has no special limitation on the vulcanization described in step (2), which can be carried out by conventional methods in the art, as long as the active metal in the hydrogenation catalyst in the oxidized state is converted into a vulcanized state, a known vulcanization method can be used, preferably the Said vulcanization is dry vulcanization or wet vulcanization.
  • the dry vulcanization and wet vulcanization described in the present invention have conventional interpretations in the field.
  • the vulcanization conditions include: a vulcanization pressure of 3.2-6.4 MPa, a vulcanization temperature of 250-400°C, a vulcanization time of 4-12 hours, and a hydrogen flow rate of 2-25mL ⁇ min -1 ⁇ g -1 .
  • the dry vulcanizing agent used in the dry vulcanization is hydrogen sulfide.
  • the sulfide gas used in the dry vulcanization includes hydrogen sulfide and hydrogen.
  • the volume content of hydrogen sulfide is 1-10%.
  • the wet vulcanization agent used in the wet vulcanization is at least one of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide.
  • the vulcanization solution used in the wet vulcanization includes the wet vulcanization agent and an organic solvent.
  • the organic solvent is at least one selected from cyclohexane, n-heptane, aviation kerosene and diesel oil.
  • the mass fraction of the wet vulcanization agent in the vulcanization solution can be selected from a wide range, preferably 2%-7%, more preferably 4%-6%.
  • the flow rate of the sulfidation solution is 0.5-5 mL ⁇ h -1 ⁇ g -1 , preferably 1-4 mL ⁇ h -1 ⁇ g -1 .
  • the amount of the Group VIB metal salt and the Group VIII metal salt is such that in the prepared catalyst, based on the total weight of the catalyst, the content of the Group VIB metal sulfide in terms of sulfide It is 10-30wt%, preferably 15-28wt%, and the content of Group VIII metal sulfide is 2-10wt%, preferably 4-8wt%. According to this requirement, those skilled in the art can properly select the consumption of the Group VIB metal salt and the Group VIII metal salt and the vulcanization conditions.
  • the amount of the catalyst precursor and the molecular sieve is such that in the prepared catalyst, based on the total weight of the catalyst, the content of the molecular sieve is 1-20wt%, preferably 1-12wt%, more preferably 1.5-8 wt%.
  • molecular sieve is added to the catalyst, and the molecular sieve is loaded on the outer surface of the catalyst instead of being kneaded with the carrier.
  • the third aspect increases the utilization rate of molecular sieves, thereby reducing the amount of molecular sieves and reducing the cost of catalysts.
  • 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 repeat them here.
  • the method of introducing molecular sieve into the catalyst precursor in step (3) is not particularly limited, it can be obtained by directly mixing the catalyst precursor and the molecular sieve, or by mixing the catalyst precursor and the molecular sieve precursor It is obtained by hydrothermal treatment after mixing.
  • the method of introducing molecular sieves into the catalyst precursor in step (3) is carried out in at least one of the following ways:
  • step (3) (a) performing hydrothermal treatment on the catalyst precursor and the molecular sieve precursor, and performing the drying and roasting in step (3) under an inert atmosphere;
  • the catalyst precursor is mixed with the ball-milled molecular sieve, and then dried and calcined in step (3).
  • the molecular sieve precursor can be hydrothermally treated to generate the above-mentioned molecular sieve gel.
  • the molecular sieve precursor includes a gel formed by mixing a silicon source and/or an aluminum source, a precipitating agent, a templating agent and water.
  • the preparation method is well known to those skilled in the art, and the molecular sieve can be formed by precipitation method or sol-gel method.
  • the type of the silicon source and/or aluminum source, precipitating agent, and template is well known to those skilled in the art, and the silicon source is preferably selected from at least one of sodium silicate, tetraethyl orthosilicate, silica sol and chromatography silica gel A sort of.
  • the aluminum source is preferably at least one selected from sodium metaaluminate, aluminum hydroxide and pseudo-boehmite.
  • the precipitating agent is preferably at least one selected from sodium hydroxide, ammonia water and potassium hydroxide.
  • the templating agent is preferably selected from cetyltrimethylammonium bromide, ethylenediamine, n-butylamine, tetrapropylammonium bromide, ethanol, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylammonium bromide, At least one of ethylamine, di-n-propylamine, diisopropylamine and methylcellulose.
  • the molecular sieve is a silica-alumina molecular sieve
  • the present invention has a wide selection range of conditions for the hydrothermal treatment, subject to the availability of the molecular sieve, preferably, the conditions for the hydrothermal treatment include: a temperature of 90-200° C., a pressure of 0.1-2 MPa, and a pH of 7.5-9, the time is 5-48 hours.
  • the particle size of the ball-milled molecular sieve is 0.1-10 nm, more preferably 0.1-5 nm.
  • the use of this preferred embodiment is more conducive to the role of molecular sieves.
  • the present invention has no special limitation on the parameters and equipment of the ball mill.
  • the drying conditions in step (3) include: a temperature of 20-90° C., and a time of 4-16 hours.
  • the conditions for the calcination in step (3) include: the temperature is 300-500° C., and the time is 2-5 hours.
  • the drying and calcining in step (3) can be carried out under an inert atmosphere.
  • inert atmosphere can be as mentioned above.
  • the third aspect of the present invention provides the application of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect in oil hydrogenation.
  • the hydrogenation catalyst provided by the invention can be applied in the hydrogenation of different oil products through the matching of different active metals and molecular sieve types. It is preferably used in oil hydrofinishing, oil hydroupgrading, oil hydrocracking or special oil hydrofinishing, and is more preferably used in polycyclic aromatic hydrocarbon hydrogenation saturation reaction.
  • the catalyst provided by the invention has high activity and selectivity, and when it is applied in the hydrogenation saturation reaction process of polycyclic aromatic hydrocarbons, it has very high hydrogenation saturation activity and selectivity of polycyclic aromatic hydrocarbons.
  • the fourth aspect of the present invention provides a method for hydrogenation of oil products, especially a method for hydrogenation saturation reaction of polycyclic aromatic hydrocarbons, comprising hydrogenation of oil products with the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the method described in the second aspect catalyst contact reaction.
  • the oil contains polycyclic aromatic hydrocarbons
  • the hydrogenation reaction includes a hydrogenation saturation reaction of polycyclic aromatic hydrocarbons.
  • the content of polycyclic aromatic hydrocarbons in the oil is preferably 5-70 wt%.
  • the hydrogenation catalyst provided by the invention is suitable for hydrogenation reaction of various oil products containing polycyclic aromatic hydrocarbons, including but not limited to diesel oil.
  • the content of polycyclic aromatic hydrocarbons in the oil product is 10-60 wt%
  • the content of single-ring aromatic hydrocarbons is 10-30 wt%
  • the content of alkanes is 10-80 wt%.
  • the oil may also contain other elements, such as sulfur and nitrogen, the content of which is not particularly limited.
  • the reaction conditions include: the pressure is 1-12MPa, more preferably 6-10MPa, the hydrogen partial pressure is preferably 50%-90% of the total pressure; the oil volume space velocity is 0.1-10h -1 , more preferably 0.5-3h -1 , the reaction temperature is 200-400°C, more preferably 330-380°C, and the hydrogen-to-oil volume ratio is 10-1000:1, more preferably 100-800:1.
  • the ratio of the amount of molecular sieves directly interacting with Group VIB metal sulfides to the total amount of molecular sieves is characterized by TEM-EDS (transmission electron microscopy-energy dispersive X-ray spectroscopy), and the specific method is as follows: described in the method section.
  • the contents of Group VIB metal sulfides and Group VIII metal sulfides can be jointly characterized by inductively coupled plasma ICP and XPS energy spectroscopy, and the specific method is as described in the detailed description.
  • the aqueous solution containing 50wt% glycerol is impregnated in the alumina carrier, then dried at 80° C. for 4 hours in N atmosphere, and roasted at 300° C. for 3 hours to obtain the pretreated carrier.
  • the carbon content in the pretreated carrier is as shown in the table 1.
  • the weight percentage of each component in the catalyst C-1 is: MoS 2 is 20%, NiS is 4.2%, Y molecular sieve is 4.0%, and the rest is alumina carrier.
  • the weight percentage of each component in the catalyst C-2 is: MoS 2 is 21%, NiS is 4.2%, ZSM-5 molecular sieve is 3.5%, and the rest is alumina carrier.
  • the aqueous solution containing 50wt% ethylene glycol is impregnated in the alumina carrier, then dried at 90°C for 4 hours in N2 atmosphere, and calcined at 300°C for 3 hours to obtain the pretreated carrier.
  • the carbon content in the pretreated carrier is as shown in the table 1.
  • the weight percentage of each component in the catalyst C-3 is: MoS 2 is 24%, NiS is 3.2%, ⁇ -type molecular sieve is 5.0%, and the rest is alumina carrier.
  • the aqueous solution containing 50wt% ethylene glycol is impregnated in the alumina carrier, then dried at 90° C. for 4 hours in N atmosphere, and roasted at 250° C. for 3 hours to obtain the pretreated carrier.
  • the carbon content in the pretreated carrier is as shown in the table 1.
  • the weight percentage of each component in the catalyst C-4 is: MoS 2 is 22%, NiS is 4.8%, MCM-41 molecular sieve is 3.8%, and the rest is alumina carrier.
  • the weight percentage of each component in the catalyst C-5 is: MoS 2 is 20%, CoS is 5.0%, Y molecular sieve is 5.0%, and the rest is alumina carrier.
  • the weight percent of each component in the catalyst C-6 is: 24% of WS 2 , 4.8% of NiS, 4.3% of ZSM-5 molecular sieve, and the rest is alumina carrier.
  • the weight percentage of each component in the catalyst C-7 is: WS 2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.
  • the difference is that the alumina carrier is replaced by zirconia to obtain catalyst C-8.
  • the difference is that in step (3), the catalyst precursor prepared in step (2) is directly mixed with the Y-type molecular sieve (particle size is 0.2-2.0nm) after ball milling, and then the drying and calcination.
  • the difference is that the content of molecular sieve is 16%, the content of MoS 2 and NiS is unchanged, and the content of alumina carrier is correspondingly reduced to obtain catalyst C-10.
  • step (2) impregnate the mixed solution of phosphomolybdic acid and nickel nitrate into the modified alumina carrier prepared in step (1), then dry at 90°C for 3 hours, and then bake at 450°C for 3 hours, then carry out vulcanization treatment, the vulcanization temperature
  • the temperature is 320°C
  • the vulcanization pressure is 3.0MPa
  • the vulcanization time is 4h, and then it is lowered to room temperature in N2 atmosphere to obtain catalyst DC-1.
  • the weight percentage of each component in the catalyst DC-1 is: MoS 2 is 20%, NiS is 4.8%, Y molecular sieve content is 6%, and the rest is alumina.
  • the weight percent of each component in the catalyst DC-2 is: WS 2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.
  • the weight percentage of each component in the catalyst DC-3 is: WS 2 is 24%, CoS is 4.8%, Y molecular sieve is 5.0%, and the rest is alumina carrier.
  • This application example illustrates the hydrogenation performance of the catalyst provided by the invention for diesel polycyclic aromatic hydrocarbons.
  • the evaluation raw material oil used is diesel raw material provided by a refinery of Sinopec. Its main properties are as follows: distillation range 200-380°C, sulfur content 1.5wt%, nitrogen content 580 ⁇ g/g, single-ring aromatics content 20wt%, The polycyclic aromatic hydrocarbon content is 26 wt%.
  • a 200mL fixed-bed hydrogenation device was used to evaluate the hydrogenation reaction performance of the catalysts provided in Examples and Comparative Examples. Evaluation reaction conditions are: operating pressure 6.4MPa, reaction temperature 370°C, hydrogen/oil volume ratio 600:1, volume space velocity 1.2h -1 , and the evaluation results of 100h reaction are shown in Table 2.
  • This application example illustrates the performance of the catalyst provided by the invention for catalyzing the hydrogenation of diesel polycyclic aromatic hydrocarbons.
  • the evaluation raw material oil used is catalytic diesel oil provided by a refinery of Sinopec. Its main properties are as follows: distillation range 200-380°C, sulfur content 2.5wt%, nitrogen content 1050 ⁇ g/g, single-ring aromatics content 20wt%, The polycyclic aromatic hydrocarbon content is 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, respectively. Evaluation reaction conditions are: operating pressure 8.4MPa, reaction temperature 360°C, hydrogen/oil volume ratio 800:1, volume space velocity 1.0h -1 , the evaluation results of 100h reaction are shown in Table 3.

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Abstract

本发明涉及油品加氢领域，涉及一种加氢催化剂及其制备方法和应用，油品加氢反应的方法，所述加氢催化剂为硫化态加氢催化剂，包括载体以及分子筛和活性组分，所述活性组分包括第VIII族金属元素中的至少一种和第VIB族金属元素中的至少一种，所述加氢催化剂采用TEM-EDS方法表征，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例为60-100％。本发明提供的加氢催化剂具有较高的活性和选择性，且可以控制多环芳烃开环不断链，生成带有长支链的单环芳烃，既可以作为乙烯裂解原料又可以作为高品质柴油产品。

Description

加氢催化剂及其制备方法和应用，油品加氢反应方法
相关申请的交叉引用
本申请要求2021年10月31日提交的中国专利申请202111278954.5的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明属于油品加氢领域，涉及一种加氢催化剂及其制备方法和应用，油品加氢反应的方法。
背景技术
在油品加工过程中，根据产品质量的需求，通常需要对油品进行加氢处理，例如柴油国Ⅵ或欧Ⅵ标准，要求柴油产品中的多环芳烃含量≯7％或≯8％，需要多环芳烃加氢饱和；例如降低柴油改质，要求降低柴油中的芳烃含量，提高柴油产品的十六烷值；例如特种油品加氢，要求特种油中的芳烃含量大幅度降低；例如提高化工原料产量，要求多产石脑油，需要进行加氢裂化多产石脑油。在这些过程中，通常采用含分子筛加氢催化剂。CN200810104303.2公开了一种改性分子筛基贵金属柴油深度加氢脱芳催化剂及其制备方法，它适用于FCC柴油加氢脱芳过程，特别适用于FCC柴油加氢改质后柴油的深度加氢脱芳，脱芳后的柴油可以作为优质柴油的调和组分。该催化剂是由改性HY分子筛为载体，贵金属Pt、Pd、Ir等活性组份构成。由于所采用工业化的HY分子筛经过改性处理得到具有微孔-介孔结构，酸性适中的载体材料以及加入了具有开环选择性的活性组分的Cr、Zn、Sn、Mo等的氧化物，使得该催化剂具有抑制深度裂化和选择开环性能的特征，该催化剂可用于柴油两段加氢改质的第二段的深度脱芳反应。其可以针对柴油进行深度脱芳，但催化剂的载体为高价格高含量的分子筛，活性金属为高价格的贵金属，价格过于昂贵，同时高含量的分子筛载体，其中大部分分子筛没有起到作用。
CN201210332369.3公开了一种加氢转化多环芳烃的方法，包括：(1)在至少一个加氢反应区，在氢气的存在下将含有多环芳烃的原料与加氢催化剂接触反应，得到一种多环芳烃至少被部分加氢饱和了的反应产物；(2)在至少一个 加氢裂解反应区，在氢气的存在下将步骤(1)得到的多环芳烃至少部分被加氢饱和了的反应产物与加氢裂解催化剂接触反应；其中，所述加氢反应区的加氢催化剂以及操作条件的选择使得含有多环芳烃的原料中的多环芳烃的转化率为40重量％以上，产物中单环加氢产物的相对收率为4-80％；所述加氢裂解反应区的加氢裂解催化剂以及操作条件的选择使得以含有多环芳烃的原料中的多环芳烃总量为基准的多环芳烃转化率为85重量％以上，产物中单环加氢裂解产物的相对收率为4-30％。该加氢转化多环芳烃的方法采用两种催化剂进行级配，且加氢裂化催化剂，其载体中的分子筛是采用混合法添加到载体中，大部分分子筛被氧化铝包裹，起不到作用，从而影响了加氢裂化催化剂的性能。
发明内容
为了克服现有加氢催化剂性能、金属活性组分利用率有待进一步提高的问题，本发明提供一种加氢催化剂及其制备方法和应用，油品加氢反应的方法。本发明提供的加氢催化剂具有较高的活性和选择性，且可以控制多环芳烃开环不断链，生成带有长支链的单环芳烃，既可以作为乙烯裂解原料又可以作为高品质柴油产品。
本发明第一方面提供一种加氢催化剂，所述加氢催化剂为硫化态加氢催化剂，包括载体以及分子筛和活性组分，所述活性组分包括第VIII族金属元素中的至少一种和第VIB族金属元素中的至少一种，所述加氢催化剂采用TEM-EDS方法表征，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例为60-100％。
优选地，以催化剂的总重量为基准，分子筛的含量为1-20wt％，优选为1-12wt％，更优选为1.5-8wt％。
本发明第二方面提供一种加氢催化剂的制备方法，该方法包括以下步骤：
(1)以含有机助剂的溶液浸渍载体，在惰性气氛下干燥和焙烧得到预处理载体；
(2)通过浸渍法向所述预处理载体引入第VIB族金属盐和第VIII族金属盐，然后进行硫化，得到催化剂前驱体；
(3)向所述催化剂前驱体引入分子筛，然后进行干燥和焙烧。
本发明第三方面提供第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂在油品加氢中的应用。
本发明第四方面提供一种油品加氢反应的方法，包括将油品与第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂接触反应。
优选地，所述油品中含有多环芳烃，所述加氢反应包括多环芳烃加氢饱和反应。
与现有技术相比，本发明提供的技术方案具有如下优势：
(1)本发明的催化剂中包括载体以及分子筛和活性组分，且更多的分子筛直接作用于活性金属，分子筛和活性金属利用率更高，更好的发挥活性作用，且有利于减少分子筛的用量，降低催化剂的成本。
(2)本发明提供的制备方法通过载体预处理-负载活性金属-硫化-负载分子筛的顺序制备催化剂，使更多的分子筛直接作用于活性金属，更好的发挥活性作用。
(3)本发明提供的制备方法在浸渍活性金属后经干燥后直接硫化，可以不进行焙烧过程，不仅降低了金属氧化物与载体之间的相互作用，且简化工艺。
附图说明
图1为本发明实施例1制得的催化剂的高分辨透射电镜图；
图2为本发明实施例1制得的催化剂的X射线衍射能谱。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，除非另有其他明确说明，否则百分比、百分含量均以质量计。
本发明第一方面提供一种加氢催化剂，所述加氢催化剂为硫化态加氢催化剂，包括载体以及分子筛和活性组分，所述活性组分包括第VIII族金属元素中 的至少一种和第VIB族金属元素中的至少一种，所述加氢催化剂采用TEM-EDS方法表征，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例为60-100％，优选为65％-95％，更优选为70％-90％，最优选为80％-90％。
本发明提供的加氢催化剂中分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例明显高于现有技术中提供的催化剂，分子筛和活性金属利用率更高，更好的发挥活性作用，且有利于减少分子筛的用量，降低催化剂的成本。
在本发明中，所述分子筛直接与第VIB族金属硫化物作用指的是分子筛负载在第VIB族金属硫化物的晶片表面。
在本发明中，所述分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例中，分子筛总量(以硅元素计)表示催化剂中分子筛的总含量，分子筛直接与第VIB族金属硫化物作用的量指的是距离第VIB族金属硫化物晶片最外层2nm以内的分子筛的含量(以硅元素计)。分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例通过TEM-EDS(透射电镜-能量弥散X射线谱)方法表征得到，采用的仪器型号为日本JEOL JEM2200FS型发射透射电子显微镜，配有扫描透射附件和美国EDAX公司X射线能谱附件。电镜加速电压200KV,STEM模式中，聚光镜光阑取2，Spote size为0.5nm。测定过程如下：将催化剂颗粒磨碎，采用悬浮法制样，将0.1g催化剂样品放入2mL容器中，用无水乙醇超声分散，取上清液，用滴管取二-三滴，滴在直径3mm样品网上，经干燥得到待测样品，然后采用TEM对待测样品进行观察分析，然后结合EDS对TEM观察到活性相(第VIB族金属硫化物晶片，如图1所示)距离边缘端点小于2nm处的Si含量进行统计分析，以Si的相应峰面积计，得到分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例。本发明分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例是通过选择40张TEM图像结合EDS分析得到的数据取平均值得到。
本发明对催化剂中分子筛的种类和含量有较宽的选择范围，可以根据不同的加氢反应进行适当的选择，通过控制分子筛的类型和含量可以实现不同的加氢目的，例如，通过控制分子筛的类型和含量可以精准控制多环芳烃的加氢饱和以及开环断链活性，催化剂灵活性高。
根据本发明的一种优选实施方式，以催化剂的总重量为基准，分子筛的含量为1-20wt％，优选为1-12wt％，更优选为1.5-8wt％，最优选为2-6wt％。本发明通过增加分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例提高分子筛的利用率，即使在较低分子筛含量下，也能够使得催化剂发挥较好的加氢性能，有利于降低催化剂的成本。
本发明对催化剂中分子筛的含量测定方法没有特别的限定，可以通过氧化硅的量结合XRD测定的分子筛的晶型进行确定，也可以通过催化剂制备过程投料计算得到。
根据本发明的一种优选实施方式，以催化剂的总重量为基准，第VIB族金属硫化物以硫化物计的含量为10-30wt％，优选15-28wt％，例如为15wt％、17wt％、20wt％、22wt％、24wt％、26wt％、28wt％，以及这些数值中的任意两个所构成的范围中的任意值；第VIII族金属硫化物以硫化物计的含量为2-10wt％，优选4-8wt％，例如为4wt％、5wt％、6wt％、7wt％、8wt％，以及这些数值中的任意两个所构成的范围中的任意值。本发明提供的加氢催化剂为一种硫化态加氢催化剂，活性组分多数以硫化物形式存在。本发明提供的催化剂中不排除含有少量第VIB族金属氧化物和第VIII族金属氧化物。
根据本发明提供的加氢催化剂，其中还可以含有其他组分，可以知晓的是，加氢催化剂中所有组分含量之和为100％。
根据本发明的一种优选实施方式，第VIB族金属元素为Mo和/或W，第VIII族金属元素为Co和/或Ni。本领域技术人员可以根据具体领域选自特定活性金属配合使用。
在本发明中，第VIB族金属硫化物可以指MoS 2、WS 2，第VIII族金属硫化物可以指CoS、NiS。
本发明中，第VIB族金属硫化物以及第VIII族金属硫化物的含量通过电感耦合等离子体ICP和XPS能谱可联合表征得到，具体地，首先通过ICP表征出催化剂中第VIB族金属的总含量和第VIII族金属的总含量，然后通过XPS能谱仪定量表征催化剂中不同价态金属元素的含量。所述XPS能谱的测量条件包括：分析室真空度≤5×10 -10mbar；制备室真空度≤1×10 -7mbar；双阳极灵敏度4.5×10 6，能量分辨1.0eV；单色器灵敏度1.4×10 5，能量分辨0.5eV。采用XPSPEAK Version 4.0分别对Mo3d、W4f、Co2p、Ni2p能谱进行拟合分峰，并且根据峰面积计算得到催化剂中不同价态金属元素的含量。
根据本发明的一种优选实施方式，所述分子筛选自Y型分子筛、ZSM-5分子筛、β型分子筛和MCM-41分子筛中的至少一种。所述分子筛可以商购得到，也可以通过现有方法合成得到，本发明对此没有特别的限定。
本发明对所述载体没有特别的限定，可以为本领域常规使用的各种载体，可以是市售的商品也可由现有技术中任意一种方法制备，例如所述载体可以为无机耐熔氧化物。优选地，所述载体选自氧化铝、氧化硅、氧化钛和氧化锆中的至少一种。综合考虑成本以及效果，优选所述载体为氧化铝。
本发明中，所述载体中还可以含有掺杂元素，所述掺杂元素例如可以为磷、硅、硼、氟、钠等元素中的一种或几种。所述掺杂元素的添加量可以为常规添加量，优选占载体质量的0.5％-6％。
本发明第二方面提供一种加氢催化剂的制备方法，该方法包括以下步骤：
(1)以含有机助剂的溶液浸渍载体，在惰性气氛下干燥和焙烧得到预处理载体；
(2)通过浸渍法向所述预处理载体引入第VIB族金属盐和第VIII族金属盐，然后进行硫化，得到催化剂前驱体；
(3)向所述催化剂前驱体引入分子筛，然后进行干燥和焙烧。
根据本发明提供的方法，通过对载体进行预处理，在载体表面形成C惰性表层，一方面能减弱金属与载体的相互作用，一方面在步骤(3)分子筛引入过程中，因载体表面覆盖C层，C层属于非极性，分子筛会更多地与金属作用，增加分子筛与活性金属直接作用的比例。
根据本发明的一种优选实施方式，所述预处理载体中碳含量为3-20wt％，优选为5-10wt％。采用该种优选实施方式不仅能够增加分子筛与活性金属直接作用的比例，还能够保证催化剂的稳定性。
本发明对所述有机助剂的种类没有特别的限定，只要能够经惰性气氛下干燥和焙烧在载体表面形成C惰性表层即可，优选所述有机助剂选自烃类、醇类、羧酸类，更优选可以选自乙二醇、丙三醇、丁二醇、戊二醇、醋酸、柠檬酸、葡萄糖、丙二酸、丁二酸、戊二酸、航煤和C9芳烃中的至少一种。
所述有机助剂的碳原子数优选为2-10。优选情况下，所述有机助剂含有羟基和/或羧基，采用该种优选实施方式更有利于活性金属的分散。
根据本发明的一种优选实施方式，所述有机助剂选自乙二醇、丙三醇、丁二醇、戊二醇、醋酸、柠檬酸、葡萄糖、丙二酸、丁二酸和戊二酸中的至少一种。
根据本发明提供的方法，所述含有机助剂的溶液中还任选地含有溶剂，本领域技术人员可以理解的是，步骤(1)只要在载体表面形成C惰性表层即可，所述含有机助剂的溶液只要满足能够浸渍到所述载体上即可，当所述有机助剂为固体有机助剂时，优选所述含有机助剂的溶液中还含有溶剂，当所述有机助剂为液体时，所述含有机助剂的溶液中可以含有溶剂，也可以不含有。
根据本发明，对所述含有机助剂的溶液中溶剂选择范围较宽，没有特别的限定，只要能够溶解所述有机助剂即可(例如水或者乙醇)，本领域技术人员可以根据具体有机助剂种类进行适当选择。
根据本发明的一种优选实施方式，含有机助剂的溶液中，当所述有机助剂为固体时，有机助剂的含量为10-30wt％。
根据本发明的一种优选实施方式，含有机助剂的溶液中，当所述有机助剂为液体时，有机助剂的含量为50-100wt％。
根据本发明，含有机助剂的溶液的用量可以根据孔饱和浸渍确定。
本发明步骤(1)所述惰性气氛指的是不参与反应的气氛，可以由惰性气体提供，所述惰性气体包括但不限于氮气、氦气、氩气和氖气中的至少一种。
本发明步骤(1)所述干燥的条件优选包括：温度为20-90℃，时间为4-16小时。
本发明步骤(1)所述焙烧的条件优选包括：温度为200-400℃，时间为3-8小时；优选地，温度为250-350℃，时间为3-5小时。
根据本发明提供的方法，所述载体以及第VIB族金属、第VIII族金属种类的选择范围可以与上述第一方面所述的加氢催化剂中载体以及第VIB族金属、第VIII族金属种类的选择范围相同，本发明在此不再赘述。
在本发明提供的方法中，对步骤(2)所述浸渍法没有特别的限定，可以为等体积浸渍，也可以为过饱和浸渍。所述第VIB族金属盐和第VIII族金属盐可以通过共浸渍同时引入预处理载体，也可以通过分步浸渍，分别引入预处理载体， 对二者引入的顺序没有特别的限定。优选地，所述第VIB族金属盐和第VIII族金属盐通过共浸渍同时引入预处理载体。优选地，步骤(2)包括：采用含有第VIB族金属盐和第VIII族金属盐的浸渍液浸渍所述预处理载体，然后进行干燥。其中，浸渍液配制方法为本领域技术人员熟知。所述干燥优选在惰性气氛下进行。所述惰性气氛的选择范围可以与上文相同，在此不再赘述。所述干燥的条件包括：温度为20-90℃，时间为4-16小时。
本发明对第VIB族金属盐和第VIII族金属盐的种类选自范围较宽，以后续能够转化为各自的金属硫化物为基准，优选地，所述的第VIB族金属盐为第VIB族金属的磷酸盐和/或铵盐，所述的第VIII族金属盐为第VIII族金属的硝酸盐、醋酸盐和硫酸盐中的至少一种。
本发明对步骤(2)所述硫化没有特别的限定，可以采用本领域常规方法进行，只要使氧化态加氢催化剂中的活性金属转化为硫化态即可，可采用公知的硫化方法，优选所述硫化为干法硫化或湿法硫化。本发明所述干法硫化、湿法硫化具有本领域常规释义。
优选地，所述硫化的条件包括：硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h，氢气的流量为2-25mL·min -1·g -1。
根据本发明的一种优选实施方式，所述干法硫化采用的干法硫化剂为硫化氢。具体地，所述干法硫化采用的硫化气包括硫化氢和氢气。优选地，硫化气中，硫化氢的体积含量为1-10％。
根据本发明的一种优选实施方式，所述湿法硫化采用的湿法硫化剂为二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种。具体地，所述湿法硫化采用的硫化液包括所述湿法硫化剂和有机溶剂。优选地，所述有机溶剂选自环己烷、正庚烷、航空煤油和柴油中的至少一种。对所述硫化液中湿法硫化剂的质量分数选择范围较宽，优选为2％-7％，更优选为4％-6％。优选硫化液的流量为0.5-5mL·h -1·g -1，优选1-4mL·h -1·g -1。
根据本发明的一种优选实施方式，第VIB族金属盐和第VIII族金属盐的用量使得制得的催化剂中，以催化剂的总重量为基准，第VIB族金属硫化物以硫化物计的含量为10-30wt％，优选15-28wt％；第VIII族金属硫化物以硫化物计的含量为2-10wt％，优选4-8wt％。本领域技术人员根据该要求，可以适当选择第 VIB族金属盐和第VIII族金属盐的用量以及硫化条件。
根据本发明，优选地，所述催化剂前驱体和分子筛的用量使得制得的催化剂中，以催化剂的总重量为基准，分子筛的含量为1-20wt％，优选为1-12wt％，更优选为1.5-8wt％。本发明提供的方法在催化剂中加入分子筛，并使分子筛负载于催化剂外表面而不是与载体混捏，一方面有利于提高分子筛与活性金属直接作用的比例，提高催化剂的加氢活性；另一方面可以通过控制分子筛的类型和含量精准控制多环芳烃的加氢饱和以及开环断链活性，催化剂灵活性高；第三方面增加了分子筛的利用率，因此降低了分子筛的用量，降低催化剂的成本。
根据本发明提供的方法，步骤(3)所述分子筛种类的选择范围可以与上述第一方面所述的加氢催化剂中分子筛种类的选择范围相同，本发明在此不再赘述。
根据本发明提供的方法，对步骤(3)向所述催化剂前驱体引入分子筛的方法没有特别的限定，可以是将催化剂前驱体与分子筛直接混合得到，也可以是将催化剂前驱体与分子筛前驱体混合后进行水热处理得到。
优选地，步骤(3)向所述催化剂前驱体引入分子筛的方法采用如下至少一种方式进行：
(a)将所述催化剂前驱体与分子筛前驱体进行水热处理，在惰性气氛下进行步骤(3)所述干燥、焙烧；
(b)在溶剂存在下，将所述催化剂前驱体与球磨后的分子筛进行混合，然后进行步骤(3)所述干燥、焙烧。
根据本发明，可以理解的是，所述分子筛前驱体可以为通过水热处理，生成上述种类分子筛的凝胶。优选地，方式(a)中，所述分子筛前驱体包括硅源和/或铝源、沉淀剂、模板剂和水混合后形成的凝胶。其配制方法为本领域技术人员熟知，可以采用沉淀法或溶胶凝胶法形成分子筛。
所述硅源和/或铝源、沉淀剂、模板剂的种类为本领域技术人员熟知，所述硅源优选选自硅酸钠、正硅酸乙酯、硅溶胶和层析硅胶中的至少一种。所述铝源优选选自偏铝酸钠、氢氧化铝和拟薄水铝石中的至少一种。所述沉淀剂优选选自氢氧化钠、氨水和氢氧化钾中的至少一种。所述模板剂优选选自十六烷基三甲基溴化铵、乙二胺、正丁胺、四丙基溴化铵、乙醇、四乙基氢氧化铵、四乙基溴化铵、三乙胺、二正丙胺、二异丙胺和甲基纤维素中的至少一种。
根据本发明，当所述分子筛为硅铝分子筛时，优选地，所述凝胶的摩尔组成为n(SiO 2):n(Al 2O 3):n(Na 2O):n(模板剂):n(H 2O)＝(5-30)：1：(1-10)：(1-10)：(100-300)。
根据本发明，当所述分子筛为全硅分子筛时，优选地，所述凝胶的摩尔组成为n(SiO 2):n(Na 2O):n(模板剂):n(H 2O)＝100：(10-30)：(10-30)：(1500-3000)。
本发明对所述水热处理的条件选择范围较宽，以能够得到所述分子筛为准，优选情况下，所述水热处理的条件包括：温度为90-200℃，压力为0.1-2MPa，pH为7.5-9，时间为5-48小时。
根据本发明，优选地，方式(b)中，球磨后的分子筛的粒径为0.1-10nm，更优选为0.1-5nm。采用该种优选实施方式更有利于发挥分子筛的作用。本发明对球磨的参数及设备没有特别的限定。
根据本发明的一种优选实施方式，步骤(3)所述干燥的条件包括：温度为20-90℃，时间为4-16小时。
根据本发明的一种优选实施方式，步骤(3)所述焙烧的条件包括：温度为300-500℃，时间为2-5小时。
步骤(3)所述干燥和焙烧可以在惰性气氛下进行。惰性气氛的具体选择可以如上文所述。
本发明第三方面提供第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂在油品加氢中的应用。
本发明提供的加氢催化剂可以通过不同活性金属以及分子筛种类的匹配实现在不同油品加氢中的应用。优选在油品加氢精制、油品加氢改质、油品加氢裂化或者特种油加氢精制中的应用，进一步优选在多环芳烃加氢饱和反应中的应用。
本发明提供的催化剂具有较高的活性和选择性，将其应用于多环芳烃加氢饱和反应过程中，具有很高的多环芳烃加氢饱和活性和选择性。
本发明第四方面提供一种油品加氢方法，特别是多环芳烃加氢饱和反应的方法，包括将油品与第一方面所述加氢催化剂或者第二方面所述方法制备的加氢催化剂接触反应。
优选地，油品中含有多环芳烃，所述加氢反应包括多环芳烃加氢饱和反应。所述油品中多环芳烃的含量优选为5-70wt％。
本发明提供的加氢催化剂适用于含有多环芳烃的各种油品进行加氢反应，包括但不限于柴油。
优选地，油品中多环芳烃含量为10-60wt％，单环芳烃含量为10-30wt％，烷烃含量为10-80wt％。所述油品中还可以含有其他元素，例如硫元素和氮元素，对其含量没有特别的限定。
优选地，反应的条件包括：压力为1-12MPa，进一步优选为6-10MPa，氢分压占总压比例优选为50％-90％；油品体积空速为0.1-10h -1，进一步优选为0.5-3h -1，反应温度为200-400℃，进一步优选为330-380℃，氢油体积比为10-1000：1，进一步优选为100-800：1。
下面结合实施例及对比例来进一步说明本发明提供的催化剂以及方法的制备过程和产品性能，但以下实施例不构成对本发明方法的限制。
以下实施例和对比例加氢催化剂中，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例采用TEM-EDS(透射电镜-能量弥散X射线谱)表征，具体方法如具体实施方式部分所述。第VIB族金属硫化物以及第VIII族金属硫化物的含量通过电感耦合等离子体ICP和XPS能谱可联合表征得到，具体方法如具体实施方式部分所述。
实施例1
(1)将含50wt％丙三醇的水溶液浸渍到氧化铝载体中，然后在N 2气氛中80℃干燥4小时，300℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸镍和七钼酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为290℃，硫化压力为3.2MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，即Y分子筛的前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在150℃、1.0MPa、pH＝8.0条件下水热处理10h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h，450焙烧3h，得到催化剂C-1。
催化剂C-1中各组分重量百分比为：MoS 2为20％，NiS为4.2％，Y分子筛为4.0％，其余为氧化铝载体。
催化剂C-1的TEM图如图1所示，XRD如图2所示，从图2可以看出，本发明提供的方法在催化剂中形成了分子筛。
实施例2
(1)将含15wt％葡萄糖的水溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，350℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸镍和七钼酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为300℃，硫化压力为3.2MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(正丁胺):n(H 2O)＝20:1:7:6:200，搅拌形成均一溶胶，即ZSM-5分子筛的前驱体，再与步骤(2)制备的催化剂前驱体混合，然后在120℃、1.0MPa、pH＝8.5条件下水热处理20h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h，450℃焙烧3h，得到催化剂C-2。
催化剂C-2中各组分重量百分比为：MoS 2为21％，NiS为4.2％，ZSM-5分子筛为3.5％，其余为氧化铝载体。
实施例3
(1)将含50wt％乙二醇的水溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，300℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸镍和七钼酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为290℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将偏铝酸钠、氢氧化钠溶解到去离子水中，然后加四乙基溴化铵，剧烈搅拌，缓慢滴加硅溶胶，陈化3h，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(四乙基溴化铵):n(H 2O)＝25:1:6:5:250，形成β型分子筛的前驱体，再与步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h，450℃焙烧3h，得到催化剂C-3。
催化剂C-3中各组分重量百分比为：MoS 2为24％，NiS为3.2％，β型分子筛为5.0％，其余为氧化铝载体。
实施例4
(1)将含50wt％乙二醇的水溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，250℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸镍和七钼酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为300℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将十六烷基三甲基溴化铵与氢氧化钠混合，再加入到去离子水中，搅拌后将正硅酸乙酯逐滴加入到混合溶液中，搅拌30min后，其中各组分摩尔比为n(SiO 2):n(Na 2O):n(十六烷基三甲基溴化铵):n(H 2O)＝11:2:2:200，形成MCM-41分子筛前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中80℃下干燥3h，500℃焙烧3h，得到催化剂C-4。
催化剂C-4中各组分重量百分比为：MoS 2为22％，NiS为4.8％，MCM-41分子筛为3.8％，其余为氧化铝载体。
实施例5
(1)将含100wt％航煤(馏程为100-220℃的常压蒸馏馏分)的溶液浸渍到氧化铝载体中，然后在N 2气氛中80℃干燥4小时，350℃焙烧3小时，得到预 处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸钴和七钼酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为300℃，硫化压力为3.2MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，即Y分子筛的前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在150℃、1.0MPa、pH＝9.0条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中80℃下干燥3h，450℃焙烧3h，得到催化剂C-5。
催化剂C-5中各组分重量百分比为：MoS 2为20％，CoS为5.0％，Y分子筛为5.0％，其余为氧化铝载体。
实施例6
(1)将含30wt％葡萄糖的水溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，350℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸镍和偏钨酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中80℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，硫化温度为300℃，氢气的流量为10mL·min -1·g -1，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(正丁胺):n(H 2O)＝20:1:7:6:200，搅拌形成均一溶胶，即ZSM-5分子筛的前驱体，再与步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中80℃下干燥3h，450℃焙烧3h，得到催化剂C-6。
催化剂C-6中各组分重量百分比为：WS 2为24％，NiS为4.8％，ZSM-5分子筛为4.3％，其余为氧化铝载体。
实施例7
(1)将含30wt％葡萄糖的水溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，300℃焙烧3小时，得到预处理载体，预处理载体中碳含量如表1所示。
(2)采用孔饱和浸渍将硝酸钴和偏钨酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，氢气的流量为10mL·min -1·g -1，硫化温度为320℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，即Y分子筛的前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h，450℃焙烧3h，得到催化剂C-7。
催化剂C-7中各组分重量百分比为：WS 2为24％，CoS为4.8％，Y分子筛为5.0％，其余为氧化铝载体。
实施例8
按照实施例1的方法，不同的是，将氧化铝载体替换为氧化锆，得到催化剂C-8。
实施例9
按照实施例1的方法，不同的是，步骤(3)中，将步骤(2)制备的催化剂前驱体直接与球磨后的Y型分子筛(粒径为0.2-2.0nm)直接混合，然后进行所述干燥和焙烧。Y型分子筛的制备包括：将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，然后在150℃、1.0MPa、pH＝8.0条件下水热处理10h；然后过滤、去离子水洗涤三次，然后在氮气气氛中90℃下干燥3h，450℃焙烧3h，得到催化剂C-9。
实施例10
按照实施例1的方法，不同的是分子筛的含量为16％，MoS 2和NiS含量不变，氧化铝载体含量相应减少，得到催化剂C-10。
对比例1
(1)将Y型分子筛与氧化铝粉、硝酸、淀粉、去离子水混合均匀，其中Y型分子筛：氧化铝粉：硝酸：淀粉：去离子水的质量比为8:92:4:3:60，然后混捏、挤条成型，然后在80℃干燥10小时，在650℃焙烧3小时，得到改性氧化铝载体，其中Y型分子筛的含量为8％。
(2)将磷钼酸和硝酸镍的混合溶液浸渍到步骤(1)制备的改性氧化铝载体中，然后在90℃干燥3小时，在450℃焙烧3小时，然后进行硫化处理，硫化温度为320℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂DC-1。
催化剂DC-1中各组分重量百分比为：MoS 2为20％，NiS为4.8％，Y分子筛含量为6％，其余为氧化铝。
对比例2
(1)将硝酸钴和偏钨酸铵的溶液浸渍到氧化铝载体，然后在氮气气氛中90℃干燥3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，硫化温度为320℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂前驱体。
(2)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，即Y分子筛的前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h得到催化剂DC-2。
催化剂DC-2中各组分重量百分比为：WS 2为24％，CoS为4.8％，Y分子筛为5.0％，其余为氧化铝载体。
对比例3
(1)将含30wt％葡萄糖的溶液浸渍到氧化铝载体中，然后在N 2气氛中90℃干燥4小时，300℃焙烧3小时，得到预处理载体。
(2)将硝酸钴和偏钨酸铵的溶液浸渍到步骤(1)制备的预处理载体，然后在氮气气氛中80℃干燥3h，400℃焙烧3h，得到催化剂前驱体。
(3)将氢氧化钠、硅溶胶、偏铝酸钠和乙二胺加入到去离子水中，其中各组分摩尔比为n(SiO 2):n(Al 2O 3):n(Na 2O):n(乙二胺):n(H 2O)＝12:1:6:3:180，搅拌至形成均一溶胶，即Y分子筛的前驱体，再和步骤(2)制备的催化剂前驱体混合，然后在130℃、1.0MPa、pH＝8.5条件下水热处理15h；然后过滤、去离子水洗涤三次，在氮气气氛中90℃下干燥3h，450℃焙烧3h，然后采用含有1.5体积％H 2S的氢气进行硫化处理，硫化温度为320℃，硫化压力为3.0MPa，硫化时间为4h，然后在N 2气氛中降至室温，得到催化剂DC-3。
催化剂DC-3中各组分重量百分比为：WS 2为24％，CoS为4.8％，Y分子筛为5.0％，其余为氧化铝载体。
以上实施例和对比例中，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例列于表1中。
表1
Figure PCTCN2022127557-appb-000001
Figure PCTCN2022127557-appb-000002
应用例1
本应用例说明本发明提供的催化剂对于柴油多环芳烃的加氢性能。
采用的评价原料油是由中石化某炼厂提供的柴油原料，其主要性质如下：馏程200-380℃，硫含量为1.5wt％，氮含量为580μg/g，单环芳烃含量为20wt％，多环芳烃含量为26wt％。采用200mL的固定床加氢装置分别对实施例和对比例提供的催化剂进行加氢反应性能评价。评价反应条件为：操作压力6.4MPa，反应温度370℃，氢/油体积比600:1，体积空速是1.2h -1，反应100h的评价结果见表2。
表2
Figure PCTCN2022127557-appb-000003
应用例2
本应用例说明本发明提供的催化剂对于催化柴油多环芳烃的加氢性能。
采用的评价原料油是由中石化某炼厂提供的催化柴油，其主要性质如下：馏程200-380℃，硫含量为2.5wt％，氮含量为1050μg/g，单环芳烃含量为20wt％，多环芳烃含量为55wt％。采用200mL的固定床加氢装置分别对实施例2、3、4提供的催化剂进行加氢反应性能评价。评价反应条件为：操作压力8.4MPa，反应温度360℃，氢/油体积比800:1，体积空速是1.0h -1，反应100h的评价结果见表3。
表3
Figure PCTCN2022127557-appb-000004

Claims (13)

  1. 一种加氢催化剂，其特征在于，所述加氢催化剂为硫化态加氢催化剂，包括载体以及分子筛和活性组分，所述活性组分包括第VIII族金属元素中的至少一种和第VIB族金属元素中的至少一种，所述加氢催化剂采用TEM-EDS方法表征，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例为60-100％。
  2. 根据权利要求1所述的催化剂，其中，以硅元素计，分子筛直接与第VIB族金属硫化物作用的量占分子筛总量的比例为65％-95％，优选为70％-90％，更优选为80％-90％。
  3. 根据权利要求1或2所述的催化剂，其中，以催化剂的总重量为基准，分子筛的含量为1-20wt％，优选为1-12wt％，更优选为1.5-8wt％；
    优选地，以催化剂的总重量为基准，第VIB族金属硫化物以硫化物计的含量为10-30wt％，优选15-28wt％；第VIII族金属硫化物以硫化物计的含量为2-10wt％，优选4-8wt％。
  4. 根据权利要求1-3中任意一项所述的催化剂，其中，第VIB族金属元素为Mo和/或W，第VIII族金属元素为Co和/或Ni；
    优选地，所述分子筛选自Y型分子筛、ZSM-5分子筛、β型分子筛和MCM-41分子筛中的至少一种；
    优选地，所述载体选自氧化铝、氧化硅、氧化钛和氧化锆中的至少一种，优选为氧化铝。
  5. 一种加氢催化剂的制备方法，其特征在于，该方法包括以下步骤：
    (1)以含有机助剂的溶液浸渍载体，在惰性气氛下干燥和焙烧得到预处理载体；
    (2)通过浸渍法向所述预处理载体引入第VIB族金属盐和第VIII族金属盐，然后进行硫化，得到催化剂前驱体；
    (3)向所述催化剂前驱体引入分子筛，然后进行干燥和焙烧。
  6. 根据权利要求5所述的制备方法，其中，所述预处理载体中碳含量为3-20wt％，优选为5-10wt％；
    优选地，步骤(1)所述有机助剂的碳原子数为2-10，优选所述有机助剂含有羟基和/或羧基，更优选所述有机助剂选自乙二醇、丙三醇、丁二醇、戊二醇、 醋酸、柠檬酸、葡萄糖、丙二酸、丁二酸和戊二酸中的至少一种。
  7. 根据权利要求5所述的制备方法，其中，所述载体选自氧化铝、氧化硅、氧化钛和氧化锆中的至少一种，优选为氧化铝；
    优选地，第VIB族金属为Mo和/或W，第VIII族金属为Co和/或Ni；
    优选地，第VIB族金属盐和第VIII族金属盐的用量使得制得的催化剂中，以催化剂的总重量为基准，第VIB族金属硫化物以硫化物计的含量为10-30wt％，优选15-28wt％；第VIII族金属硫化物以硫化物计的含量为2-10wt％，优选4-8wt％。
  8. 根据权利要求5-7中任意一项所述的制备方法，其中，步骤(2)所述硫化为干法硫化或湿法硫化；
    优选地，干法硫化采用的为硫化氢，湿法硫化采用的湿法硫化剂为二硫化碳、二甲基二硫醚、甲基硫醚和正丁基硫醚中的至少一种；
    优选地，步骤(2)所述硫化的条件包括：硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h，氢气的流量为2-25mL·min -1·g -1。
  9. 根据权利要求5-8中任意一项所述的制备方法，其中，所述催化剂前驱体和分子筛的用量使得制得的催化剂中，以催化剂的总重量为基准，分子筛的含量为1-20wt％，优选为1-12wt％，更优选为1.5-8wt％；
    优选地，所述分子筛选自Y型分子筛、ZSM-5分子筛、β型分子筛和MCM-41分子筛中的至少一种。
  10. 根据权利要求5-9中任意一项所述的制备方法，其中，步骤(3)向所述催化剂前驱体引入分子筛的方法采用如下至少一种方式进行：
    (a)将所述催化剂前驱体与分子筛前驱体进行水热处理，在惰性气氛下进行步骤(3)所述干燥、焙烧；
    (b)在溶剂存在下，将所述催化剂前驱体与球磨后的分子筛进行混合，然后进行步骤(3)所述干燥、焙烧。
  11. 根据权利要求10所述的制备方法，其中，
    方式(a)中，所述分子筛前驱体包括硅源和/或铝源、沉淀剂、模板剂和水混合后形成的凝胶；
    优选地，所述水热处理的条件包括：温度为90-200℃，压力为0.1-2MPa， pH为7.5-9，时间为5-48小时；
    优选地，方式(b)中，球磨后的分子筛的粒径为0.1-10nm，更优选为0.1-5nm。
  12. 权利要求1-4中任意一项所述的加氢催化剂或者权利要求5-11中任意一项制备方法制得的加氢催化剂在油品加氢中的应用，优选在油品加氢精制、油品加氢改质、加氢裂化或者特种油加氢精制中的应用，进一步优选在多环芳烃加氢饱和反应中的应用。
  13. 一种油品加氢反应的方法，包括将油品与权利要求1-4中任意一项所述的加氢催化剂或者权利要求5-11中任意一项制备方法制得的加氢催化剂接触反应；
    优选地，所述油品中含有多环芳烃，所述加氢反应包括多环芳烃加氢饱和反应；
    优选地，反应的条件包括：压力为1-12MPa，氢分压占总压比例优选为50％-90％；油品体积空速为0.1-10h -1，反应温度为200-400℃，氢油体积比为10-1000：1。
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